Fungicidal pyrazoles

ABSTRACT

Disclosed are compounds of Formula 1, including all geometric and stereoisomers, N-oxides, and salts thereof, 
     
       
         
         
             
             
         
       
     
     wherein
         Q 1  is a phenyl ring, naphthalenyl ring system, a 5- to 6-membered fully unsaturated heterocyclic ring or an 8- to 10-membered heteroaromatic bicyclic ring system, each as described with optional substituents as defined in the disclosure;   Q 2  is a phenyl ring, a naphthalenyl ring system, a 5- to 6-membered saturated, partially unsaturated or fully unsaturated heterocyclic ring, or an 8- to 10-membered heteroaromatic bicyclic ring system, each as described with optional substituents as defined in the disclosure;   X is O, S(O) m , NR 4 , CR 15 R 16 , C(═O) or C(═S);   and R 1 , R 1a , R 2 , R 4 , R 15 , R 16  and m are as defined in the disclosure.       

     Also disclosed are compositions containing the compounds of Formula 1 and methods for controlling plant disease caused by a fungal pathogen comprising applying an effective amount of a compound or a composition of the invention. Also disclosed are compounds of Formula 2, including all geometric and stereoisomers, and salts thereof, 
     
       
         
         
             
             
         
       
     
     wherein
         X is NH; and   Q 1 , Q 2  and R 2  are as defined for Formula 1;
 
which are useful as intermediates for preparing compounds of Formula 1.

FIELD OF THE INVENTION

This invention relates to certain pyrazoles, their N-oxides, salts andcompositions, and methods of their use as fungicides.

BACKGROUND OF THE INVENTION

The control of plant diseases caused by fungal plant pathogens isextremely important in achieving high crop efficiency. Plant diseasedamage to ornamental, vegetable, field, cereal, and fruit crops cancause significant reduction in productivity and thereby result inincreased costs to the consumer. Many products are commerciallyavailable for these purposes, but the need continues for new compoundswhich are more effective, less costly, less toxic, environmentally saferor have different sites of action. JP09208620 disclosesN-phenylpyrazolylamine and N-pyridylpyrazolylamine derivatives asinsecticides, herbicides and fungicides; however the fungicides of thepresent invention are not disclosed in this publication.

SUMMARY OF THE INVENTION

This invention is directed to compounds of Formula 1 (including allgeometric and stereoisomers), N-oxides, and salts thereof, agriculturalcompositions containing them and their use as fungicides:

wherein

-   -   Q¹ is a phenyl ring or a naphthalenyl ring system, each ring or        ring system optionally substituted with up to 5 substituents        independently selected from R³; or a 5- to 6-membered fully        unsaturated heterocyclic ring or an 8- to 10-membered        heteroaromatic bicyclic ring system, each ring or ring system        containing ring members selected from carbon atoms and up to 4        heteroatoms independently selected from up to 2 O, up to 2 S and        up to 4 N atoms, wherein up to 3 carbon ring members are        independently selected from C(═O) and C(═S), and the sulfur atom        ring members are independently selected from        S(═O)_(u)(═NR¹⁴)_(v), each ring or ring system optionally        substituted with up to 5 substituents independently selected        from R³ on carbon atom ring members and selected from cyano,        C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆ cycloalkyl,        C₁-C₆ alkoxy, C₂-C₆ alkoxyalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆        alkoxycarbonyl, C₂-C₆ alkylaminoalkyl and C₃-C₆        dialkylaminoalkyl on nitrogen atom ring members;    -   Q² is a phenyl ring or a naphthalenyl ring system, each ring or        ring system optionally substituted with up to 5 substituents        independently selected from R³; or a 5- to 6-membered saturated,        partially unsaturated or fully unsaturated heterocyclic ring or        an 8- to 10-membered heteroaromatic bicyclic ring system, each        ring or ring system containing ring members selected from carbon        atoms and up to 4 heteroatoms independently selected from up to        2 O, up to 2 S and up to 4 N atoms, wherein up to 3 carbon ring        members are independently selected from C(═O) and C(═S), and the        sulfur atom ring members are independently selected from        S(═O)_(u)(═NR¹⁴)_(v), each ring or ring system optionally        substituted with up to 5 substituents independently selected        from R³ on carbon atom ring members and selected from cyano,        C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆ cycloalkyl,        C₁-C₆ alkoxy, C₂-C₆ alkoxyalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆        alkoxycarbonyl, C₂-C₆ alkylaminoalkyl and C₃-C₆        dialkylaminoalkyl on nitrogen atom ring members; or C₁-C₁₂        alkyl, C₂-C₁₂ alkenyl, C₂-C₁₂ alkynyl, C₃-C₁₂ cycloalkyl or        C₃-C₁₂ cycloalkenyl, each optionally substituted with up to 5        substituents independently selected from R³;    -   X is O, S(O)_(m), NR⁴, CR¹⁵R¹⁶, C(═O) or C(═S);    -   R¹ is H, halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₄ alkenyl,        C₂-C₄ alkynyl, C₃-C₇ cycloalkyl, CO₂R⁵, C(O)NR⁶R⁷, cyano, C₁-C₆        alkoxy, C₁-C₆ haloalkoxy or C₂-C₅ alkoxyalkyl; or    -   R¹ is phenyl optionally substituted with up to 3 R⁸; or a five-        or six-membered nitrogen-containing aromatic heterocycle        optionally substituted with up to 3 substituents independently        selected from R^(9a) on carbon atom ring members and R^(9b) on        nitrogen atom ring members;    -   R^(1a) is H; or    -   R^(1a) and R¹ are taken together with the carbon atom to which        they are attached to form a cyclopropyl ring optionally        substituted with up to 2 substituents independently selected        from halogen and methyl;    -   R² is CH₃, CH₂CH₃, halogen, cyano, cyanomethyl, halomethyl,        hydroxymethyl, methoxy or methylthio; or cyclopropyl optionally        substituted with up to 2 substituents independently selected        from halogen and methyl;    -   each R³ is independently selected from halogen, cyano, nitro,        amino, methylamino, dimethylamino, formylamino, C₂-C₃        alkylcarbonylamino, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₃ alkoxy,        C₁-C₃ haloalkoxy, C₁-C₃ alkylthio, C₁-C₃ haloalkylthio, C₁-C₃        alkylsulfinyl, C₁-C₃ haloalkylsulfinyl, C₁-C₃ alkylsulfonyl,        C₁-C₃ haloalkylsulfonyl, C₁-C₂ alkylsulfonyloxy, C₁-C₂        haloalkylsulfonyloxy, C₃-C₄ cycloalkyl, C₃-C₇ cycloalkoxy, C₄-C₆        alkylcycloalkyl, C₄-C₆ cycloalkylalkyl, C₃-C₇ halocycloalkyl,        C₂-C₄ alkenyl, C₂-C₄ alkynyl, hydroxy, formyl, C₂-C₃        alkylcarbonyl, C₂-C₃ alkylcarbonyloxy, —SF₅, —SCN, C(═S)NR¹⁹R²⁰        or —U—V-T;    -   R⁴ is H, formyl, C₂-C₅ alkenyl, C₃-C₅ alkynyl, C₃-C₇ cycloalkyl,        —SO₃ ⁻M⁺, —S(═O)_(t)R¹⁰, —(C═W)R¹¹, NH₂ or OR²¹; or C₁-C₆ alkyl        or C₁-C₆ haloalkyl, each optionally substituted with up to 2        R¹²;    -   R⁵ is H, C₁-C₆ alkyl or C₁-C₆ haloalkyl;    -   R⁶ and R⁷ are independently selected from H, C₁-C₆ alkyl, C₁-C₆        haloalkyl, C₃-C₇ cycloalkyl, C₄-C₈ cycloalkylalkyl and C₄-C₈        alkylcycloalkyl; or    -   R⁶ and R⁷ are taken together with the nitrogen atom to which        they are connected to form a four- to seven-membered nonaromatic        heterocyclic ring containing ring members, in addition to the        connecting ring nitrogen atom, selected from carbon atoms and        optionally up to one ring member selected from O, S(O)_(n) and        NR¹³;    -   each R⁸, R^(9a) and R^(9b) is independently selected from        halogen, C₁-C₂ alkyl, C₁-C₂ haloalkyl, C₁-C₂ alkoxy, C₁-C₂        haloalkoxy, cyano, nitro, SCH₃, S(O)CH₃ and S(O)₂CH₃;    -   R¹⁰ is C₁-C₆ alkyl or C₁-C₆ haloalkyl;    -   each R¹¹ is independently C₁-C₆ alkyl, C₁-C₆ alkoxy, C₂-C₇        alkoxyalkyl, C₂-C₇ alkylaminoalkyl, C₂-C₈ dialkylaminoalkyl,        C₁-C₆ alkylthio or C₂-C₇ alkylthioalkyl;    -   each R¹² is independently C₃-C₇ cycloalkyl, C₁-C₄ alkoxy, C₁-C₄        haloalkoxy, C₁-C₄ alkylthio, C₁-C₄ alkylsulfinyl, C₁-C₄        alkylsulfonyl or cyano;    -   R¹³ is H, C₁-C₃ alkyl or C₂-C₃ haloalkyl;    -   each R¹⁴ is independently H, cyano, C₁-C₃ alkyl or C₁-C₃        haloalkyl;    -   R¹⁵ is H, C₁-C₄ alkyl or OR¹⁸;    -   R¹⁶ is C₁-C₄ alkyl or OR¹⁸; or    -   R¹⁵ and R¹⁶ are taken together as —OCH₂CH₂O—;    -   each R¹⁸ is independently H, formyl, C₃-C₇ cycloalkyl, —SO₃ ⁻M⁺        or —(C═W)R¹¹; or C₁-C₆ alkyl or C₁-C₆ haloalkyl, each optionally        substituted with up to 2 R¹²;    -   each R¹⁹ and R²⁰ is independently H or CH₃;    -   R²¹ is H, formyl, C₃-C₇ cycloalkyl, —SO₃ ⁻M⁺ or —(C═W)R¹¹; or        C₁-C₆ alkyl or C₁-C₆ haloalkyl, each optionally substituted with        up to 2 R¹²;    -   each U is independently O, S(═O)_(w), NR²² or a direct bond;    -   each V is independently C₁-C₆ alkylene, C₂-C₆ alkenylene, C₃-C₆        alkynylene, C₃-C₆ cycloalkylene or C₃-C₆ cycloalkenylene,        wherein up to 3 carbon atoms are independently selected from        C(═O), each optionally substituted with up to 5 substituents        independently selected from halogen, cyano, nitro, hydroxy,        C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆ alkoxy and C₁-C₆ haloalkoxy;    -   each T is independently cyano, NR^(23a)R^(23b), OR²⁴ or        S(═O)_(y)R²⁵    -   each R²² is independently H, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆        alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-C₆ (alkylthio)carbonyl,        C₂-C₆ alkoxy(thiocarbonyl), C₄-C₈ cycloalkylcarbonyl, C₄-C₈        cycloalkoxycarbonyl, C₄-C₈ (cycloalkylthio)carbonyl or C₄-C₈        cycloalkoxy(thiocarbonyl);    -   each R^(23a) and R^(23b) is independently H, C₁-C₆ alkyl, C₁-C₆        haloalkyl, C₂-C₆ alkenyl, C₃-C₆ alkynyl, C₃-C₆ cycloalkyl, C₃-C₆        halocycloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-C₆        (alkylthio)carbonyl, C₂-C₆ alkoxy(thiocarbonyl), C₄-C₈        cycloalkylcarbonyl, C₄-C₈ cycloalkoxycarbonyl, C₄-C₈        (cycloalkylthio)carbonyl or C₄-C₈ cycloalkoxy(thiocarbonyl); or    -   a pair of R^(23a) and R^(23b) attached to the same nitrogen atom        are taken together with the nitrogen atom to form a 3- to        6-membered heterocyclic ring, the ring optionally substituted        with up to 5 substituents independently selected from R²⁶;    -   each R²⁴ and R²⁵ is independently H, C₁-C₆ alkyl, C₁-C₆        haloalkyl, C₂-C₆ alkenyl, C₃-C₆ alkynyl, C₃-C₆ cycloalkyl, C₃-C₆        halocycloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-C₆        (alkylthio)carbonyl, C₂-C₆ alkoxy(thiocarbonyl), C₄-C₈        cycloalkylcarbonyl, C₄-C₈ cycloalkoxycarbonyl, C₄-C₈        (cycloalkylthio)carbonyl or C₄-C₈ cycloalkoxy(thiocarbonyl);    -   each R²⁶ is independently halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl        or C₁-C₆ alkoxy;    -   each W is independently O or S;    -   each M⁺ is independently a cation;    -   m is 0, 1 or 2;    -   n is 0, 1 or 2;    -   t is 0, 1 or 2;    -   each u and v are independently 0, 1 or 2 in each instance of        S(═O)_(u)(═NR¹⁴)_(v), provided that the sum of u and v is 0, 1        or 2;    -   each w is independently 0, 1 or 2; and    -   each y is independently 0, 1 or 2;        provided that:    -   when Q² is a phenyl ring substituted on at least one ortho        position with a substituent selected from —U—V-T wherein U is a        direct bond, V is C(═O) and T is NR^(23a)R^(23b) or OR²⁴, then X        is other than NR⁴.

More particularly, this invention pertains to a compound of Formula 1(including all geometric and stereoisomers), an N-oxide or a saltthereof.

This invention also relates to a fungicidal composition comprising acompound of Formula 1, an N-oxide, or a salt thereof, and at least oneadditional component selected from the group consisting of surfactants,solid diluents and liquid diluents.

This invention also relates to a fungicidal composition comprising: (a)a compound of Formula 1, an N-oxide, or a salt thereof, and (b) at leastone other fungicide (e.g., at least one other fungicide having adifferent site of action).

This invention further relates to a method for controlling plantdiseases caused by fungal plant pathogens comprising applying to theplant or portion thereof, or to the plant seed, a fungicidally effectiveamount of a compound of the invention (e.g., as a composition describedherein).

This invention also relates to a composition comprising a compound ofFormula 1, an N-oxide, or a salt thereof, and at least one invertebratepest control compound or agent.

The invention also relates to compounds of Formula 2 (including allgeometric and stereoisomers) and salts thereof

wherein

-   -   X is NH; and    -   Q¹, Q² and R² are as defined above for Formula 1;        provided that:    -   (a) when Q² is a phenyl ring substituted on at least one ortho        position with a substituent selected from —U—V-T wherein U is a        direct bond and T is NR^(23a)R^(23b) or OR²⁴, then V is other        than C(═O); and    -   (b) when Q¹ is phenyl and Q² is 4-(trifluoromethyl)phenyl, then        R² is other than methyl;        and to use of said compounds as intermediates for preparing        compounds of Formula 1. More particularly, the present invention        pertains to a compound of Formula 2 or a salt thereof.

DETAILS OF THE INVENTION

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having,” “contains”, “containing,” “characterizedby” or any other variation thereof, are intended to cover anon-exclusive inclusion, subject to any limitation explicitly indicated.For example, a composition, mixture, process or method that comprises alist of elements is not necessarily limited to only those elements butmay include other elements not expressly listed or inherent to suchcomposition, mixture, process or method.

The transitional phrase “consisting of” excludes any element, step, oringredient not specified. If in the claim, such would close the claim tothe inclusion of materials other than those recited except forimpurities ordinarily associated therewith. When the phrase “consistingof” appears in a clause of the body of a claim, rather than immediatelyfollowing the preamble, it limits only the element set forth in thatclause; other elements are not excluded from the claim as a whole.

The transitional phrase “consisting essentially of” is used to define acomposition or method that includes materials, steps, features,components, or elements, in addition to those literally disclosed,provided that these additional materials, steps, features, components,or elements do not materially affect the basic and novelcharacteristic(s) of the claimed invention. The term “consistingessentially of” occupies a middle ground between “comprising” and“consisting of”.

Where applicants have defined an invention or a portion thereof with anopen-ended term such as “comprising,” it should be readily understoodthat (unless otherwise stated) the description should be interpreted toalso describe such an invention using the terms “consisting essentiallyof” or “consisting of.”

Further, unless expressly stated to the contrary, “or” refers to aninclusive or and not to an exclusive or. For example, a condition A or Bis satisfied by any one of the following: A is true (or present) and Bis false (or not present), A is false (or not present) and B is true (orpresent), and both A and B are true (or present).

Also, the indefinite articles “a” and “an” preceding an element orcomponent of the invention are intended to be nonrestrictive regardingthe number of instances (i.e. occurrences) of the element or component.Therefore “a” or “an” should be read to include one or at least one, andthe singular word form of the element or component also includes theplural unless the number is obviously meant to be singular.

As referred to in the present disclosure and claims, “plant” includesmembers of Kingdom Plantae, particularly seed plants (Spermatopsida), atall life stages, including young plants (e.g., germinating seedsdeveloping into seedlings) and mature, reproductive stages (e.g., plantsproducing flowers and seeds). Portions of plants include geotropicmembers typically growing beneath the surface of the growing medium(e.g., soil), such as roots, tubers, bulbs and corms, and also membersgrowing above the growing medium, such as foliage (including stems andleaves), flowers, fruits and seeds.

As referred to herein, the term “seedling”, used either alone or in acombination of words means a young plant developing from the embryo of aseed.

As used herein, the term “alkylating agent” refers to a chemicalcompound in which a carbon-containing radical is bound through a carbonatom to leaving group such as halide or sulfonate, which is displaceableby bonding of a nucleophile to said carbon atom. Unless otherwiseindicated, the term “alkylating” does not limit the carbon-containingradical to alkyl; the carbon-containing radicals in alkylating agentsinclude the variety of carbon-bound substituent radicals specified forR¹.

Generally when a molecular fragment (i.e. radical) is denoted by aseries of atom symbols (e.g., C, H, N, O, S) the implicit point orpoints of attachment will be easily recognized by those skilled in theart. In some instances herein, particularly when alternative points ofattachment are possible, the point or points of attachment may beexplicitly indicated by a hyphen (“-”). For example, “—SCN” indicatesthat the point of attachment is the sulfur atom (i.e. thiocyanato, notisothiocyanato).

In the above recitations, the term “alkyl”, used either alone or incompound words such as “alkylthio” or “haloalkyl” includesstraight-chain or branched alkyl, such as, methyl, ethyl, n-propyl,i-propyl, or the different butyl, pentyl or hexyl isomers. “Alkenyl”includes straight-chain or branched alkenes such as ethenyl, 1-propenyl,2-propenyl, and the different butenyl isomers. “Alkenyl” also includespolyenes such as 1,2-propadienyl. “Alkynyl” includes straight-chain orbranched alkynes such as ethynyl, 1-propynyl, 2-propynyl and thedifferent butynyl isomers. “Alkenylene” denotes a straight-chain orbranched alkenediyl containing one olefinic bond. Examples of“alkenylene” include CH═CH, CH₂CH═CH, CH═C(CH₃). “Alkynylene” denotes astraight-chain or branched alkynediyl containing one triple bond.Examples of “alkynylene” include CH₂C≡C, C≡CCH₂ and the differentbutynylene, pentynylene and hexynylene isomers.

“Alkoxy” includes, for example, methoxy, ethoxy, n-propyloxy,isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.“Alkoxyalkyl” denotes alkoxy substitution on alkyl. Examples of“alkoxyalkyl” include CH₃OCH₂, CH₃OCH₂CH₂, CH₃CH₂OCH₂, CH₃CH₂CH₂CH₂OCH₂and CH₃CH₂OCH₂CH₂. “Alkylthio” includes branched or straight-chainalkylthio moieties such as methylthio, ethylthio, and the differentpropylthio, butylthio, pentylthio and hexylthio isomers. “Alkylsulfinyl”includes both enantiomers of an alkylsulfinyl group. Examples of“alkylsulfinyl” include CH₃S(O)—, CH₃CH₂S(O)—, CH₃CH₂CH₂S(O)—,(CH₃)₂CHS(O)— and the different butylsulfinyl isomers. Examples of“alkylsulfonyl” include CH₃S(O)₂—, CH₃CH₂S(O)₂—, CH₃CH₂CH₂S(O)₂—,(CH₃)₂CHS(O)₂—, and the different butylsulfonyl isomers.“Alkylthioalkyl” denotes alkylthio substitution on alkyl. Examples of“alkylthioalkyl” include CH₃SCH₂, CH₃SCH₂CH₂, CH₃CH₂SCH₂,CH₃CH₂CH₂CH₂SCH₂ and CH₃CH₂SCH₂CH₂. “(Alkylthio)carbonyl” denotes astraight-chain or branched alkylthio group bonded to a C(═O) moiety.Examples of “(alkylthio)carbonyl” include CH₃SC(═O), CH₃CH₂CH₂SC(═O) and(CH₃)₂CHSC(═O). “Alkoxy(thiocarbonyl)” denotes a straight-chain orbranched alkoxy group bonded to a C(═S) moiety. Examples of“alkoxy(thiocarbonyl)” include CH₃OC(═S), CH₃CH₂CH₂OC(═S) and(CH₃)₂CHOC(═S). “Alkylaminoalkyl” denotes a straight-chain or branchedalkyl moieties bonded to a nitrogen atom of an amino(straight-chain orbranched)alkyl moiety. Examples of “alkylaminoalkyl” include CH₃NHCH₂—,(CH₃)₂CHNHCH₂— and CH₃NHCH(CH₃)—. “Dialkylaminoalkyl” denotes twoindependent straight-chain or branched alkyl moieties bonded to anitrogen atom of an amino(straight-chain or branched)alkyl moiety.Examples of “dialkylaminoalkyl” include (CH₃)₂NCH₂—, (CH₃)₂CH(CH₃)NCH₂—and (CH₃)₂NCH(CH₃)—. The term “alkylcarbonylamino” denotes alkyl bondedto a C(═O)NH moiety. Examples of “alkylcarbonylamino” includeCH₃CH₂C(═O)NH and CH₃CH₂CH₂C(═O)NH.

“Cycloalkyl” includes, for example, cyclopropyl, cyclobutyl, cyclopentyland cyclohexyl. The term “alkylcycloalkyl” denotes alkyl substitution ona cycloalkyl moiety and includes, for example, ethylcyclopropyl,i-propylcyclobutyl, 3-methylcyclopentyl and 4-methylcyclohexyl. The term“cycloalkylalkyl” denotes cycloalkyl substitution on an alkyl moiety.Examples of “cycloalkylalkyl” include cyclopropylmethyl,cyclopentylethyl, and other cycloalkyl moieties bonded to straight-chainor branched alkyl groups. The term “cycloalkoxy” denotes cycloalkyllinked through an oxygen atom such as cyclopentyloxy and cyclohexyloxy.“Cycloalkenyl” includes carbocyclic rings that contain only one doublebond such as cyclopentenyl and cyclohexenyl, as well as carbocyclicrings with more than one double bond such as 1,3- and1,4-cyclohexadienyl, but are not aromatic. “Cycloalkylcarbonyl” denotescycloalkyl bonded to a C(═O) group including, for example,cyclopropylcarbonyl and cyclopentylcarbonyl. The term“cycloalkoxycarbonyl” means cycloalkoxy bonded to a C(═O) group, forexample, cyclopropyloxycarbonyl and cyclopentyloxycarbonyl. Theterm“cycloalkylene” denotes a cycloalkanediyl ring. Examples of“cycloalkylene” include cyclopropylene, cyclobutylene, cyclopentyleneand cyclohexylene. The term“cycloalkenylene” denotes a cycloalkenediylring containing one olefinic bond. Examples of “cycloalkenylene” includecylopropenediyl and cyclpentenediyl.

The term “halogen”, either alone or in compound words such as“haloalkyl”, or when used in descriptions such as “alkyl substitutedwith halogen” includes fluorine, chlorine, bromine or iodine. Further,when used in compound words such as “haloalkyl”, or when used indescriptions such as “alkyl substituted with halogen” said alkyl may bepartially or fully substituted with halogen atoms which may be the sameor different. Examples of “haloalkyl” or “alkyl substituted withhalogen” include F₃C—, ClCH₂—, CF₃CH₂— and CF₃CCl₂—. The terms“halocycloalkyl”, “haloalkoxy”, “haloalkylthio”, and the like, aredefined analogously to the term “haloalkyl”. Examples of “haloalkoxy”include CH₂FO—, CHF₂O—, CF₃O—, CCl₃CH₂O—, HCF₂CH₂CH₂O— and CF₃CH₂O—.Examples of “fluoroalkoxy” include CH₂FO—, CHF₂O—, CF₃O— HCF₂CH₂CH₂O—and CF₃CH₂O—. Examples of “fluoromethoxy” include CH₂FO—, CHF₂O— andCF₃O—. Examples of “haloalkylthio” include CCl₃S—, CF₃S—, CCl₃CH₂S— andClCH₂CH₂CH₂S—. Examples of “haloalkylsulfinyl” include CF₃S(O)—,CCl₃S(O)—, CF₃CH₂S(O)— and CF₃CF₂S(O)—. Examples of “haloalkylsulfonyl”include CF₃S(O)₂—, CCl₃S(O)₂—, CF₃CH₂S(O)₂— and CF₃CF₂S(O)₂—.

The total number of carbon atoms in a substituent group is indicated bythe “C_(i)-C_(j)” prefix where i and j are numbers from 1 to 12. Forexample, C₁-C₄ alkylsulfonyl designates methylsulfonyl throughbutylsulfonyl; C₂ alkoxyalkyl designates CH₃OCH₂—; C₃ alkoxyalkyldesignates, for example, CH₃CH(OCH₃)—, CH₃OCH₂CH₂— or CH₃CH₂OCH₂—; andC₄ alkoxyalkyl designates the various isomers of an alkyl groupsubstituted with an alkoxy group containing a total of four carbonatoms, examples including CH₃CH₂CH₂OCH₂— and CH₃CH₂OCH₂CH₂—.

As used herein, the following definitions shall apply unless otherwiseindicated. The term “optionally substituted” is used interchangeablywith the phrase “substituted or unsubstituted” or with the term“(un)substituted.” Unless otherwise indicated, an optionally substitutedgroup may have a substituent at each substitutable position of thegroup, and each substitution is independent of the other.

The term “unsubstituted” in connection with a group such as a ring orring system means the group does not have any substituents other thanits one or more attachments to the remainder of Formula 1. The term“optionally substituted” means that the number of substituents can bezero. Unless otherwise indicated, optionally substituted groups may besubstituted with as many optional substituents as can be accommodated byreplacing a hydrogen atom with a non-hydrogen substituent on anyavailable carbon or nitrogen atom. The number of optional substituentsmay be restricted by an expressed limitation. For example, the phrase“optionally substituted with up to 3 substituents selected from R^(9a)on carbon ring members” means that 0, 1, 2 or 3 substituents can bepresent (if the number of potential connection points allows).Similarly, the phrase “optionally substituted with up to 5 substituentsselected from R³ on carbon ring members” means that 0, 1, 2, 3, 4 or 5substituents can be present if the number of available connection pointsallows. When a range specified for the number of substituents (e.g., rbeing an integer from 0 to 4 or from 0 to 3 for 5- and 6-memberednitrogen-containing heterocycles in Exhibit A) exceeds the number ofpositions available for substituents on a ring (e.g., 2 positionsavailable for (R^(a))_(r) on U-27 in Exhibit A), the actual higher endof the range is recognized to be the number of available positions.

When a compound is substituted with a substituent bearing a subscriptthat indicates the number of said substituents can exceed 1, saidsubstituents (when they exceed 1) are independently selected from thegroup of defined substituents, e.g., (R³)_(p) in Table 1 where p is 0,1, 2, 3, 4 or 5. When a group contains a substituent which can behydrogen, for example R¹, R⁴, R⁵, R⁶, R⁷ or R¹³, then when thissubstituent is taken as hydrogen, it is recognized that this isequivalent to said group being unsubstituted. When a variable group isshown to be optionally attached to a position, for example (R^(a))_(r)in H-23 of Exhibit 1, wherein r may be 0, then hydrogen may be at theposition even if not recited in the variable group definition. When oneor more positions on a group are said to be “not substituted” or“unsubstituted”, then hydrogen atoms are attached to take up any freevalency.

The variables “m”, “n”, “t”, “u”, “v”, “w” and “y” in the Summary of theInvention and corresponding parts of the patent specification relate tosubscripts appearing to the right of atoms or other molecular fragmentswithin parentheses and denote the integral number of instances presentof the atoms or other molecular fragments within the parentheses. “m”relates to “S(O)_(m)”, “n” relates to “S(O)_(n)”, “t” relates to“—S(═O)_(t)R¹⁰”, “u” and “v” relate to “S(═O)_(u)(═NR¹⁴”, “w” relates to“S(═O)_(w)”, and “y” relates to “S(═O)_(y)R²⁵. For example, “m” being 0,1 or 2 means that “S(O)_(m)” can be “S”, “S(O)” or “S(O)₂”.

Unless otherwise indicated, a “ring” as a component of Formula 1 iscarbocyclic or heterocyclic. The term “ring system” as a component ofFormula 1 denotes two fused rings (e.g., a phenyl ring fused to apyridinyl ring to form quinolinyl). The term “ring member” refers to anatom or other moiety (e.g., O, S(O), S(O)₂ or S(═O)_(u)(═NR¹⁴)_(v))forming the backbone of a ring or ring system.

The term “carbocyclic ring” denotes a ring wherein the atoms forming thering backbone are selected only from carbon. Unless otherwise indicated,a carbocyclic ring can be a saturated, partially unsaturated, or fullyunsaturated ring. “Saturated carbocyclic” refers to a ring having abackbone consisting of carbon atoms linked to one another by singlebonds; unless otherwise specified, the remaining carbon valences areoccupied by hydrogen atoms.

The terms “heterocyclic ring” or “heterocycle” denote a ring or ringsystem in which at least one atom forming the ring backbone is notcarbon, e.g., nitrogen, oxygen or sulfur. Typically a heterocyclic ringcontains no more than 4 nitrogens, no more than 2 oxygens and no morethan 2 sulfurs. Unless otherwise indicated, a heterocyclic ring can be asaturated, partially unsaturated, or fully unsaturated ring. The term“saturated heterocyclic ring” refers to a heterocyclic ring containingonly single bonds between ring members. In regards to degree ofsaturation, “a partially unsaturated heterocyclic ring” is intermediatebetween a saturated heterocyclic ring and a fully unsaturatedheterocyclic ring (which may be aromatic). Therefore, as referred to inthe present disclosure and claims, the term “partially unsaturatedheterocyclic ring” denotes a heterocyclic ring comprising at least onering member bonded to an adjacent ring member through a double bond andwhich conceptually potentially accommodates a number of non-cumulateddouble bonds between adjacent ring members (i.e. in its fullyunsaturated counterpart form) greater than the number of double bondspresent (i.e. in its partially unsaturated form). When a fullyunsaturated heterocyclic ring satisfies Hickel's rule, then said ring isalso called a “heteroaromatic ring” or “aromatic heterocyclic ring”. Theterms “heteroaromatic ring system” and “heteroaromatic bicyclic ringsystem” denote a ring system in which at least one atom forming the ringbackbone is not carbon, e.g., nitrogen, oxygen or sulfur, and at leastone ring is aromatic. Unless otherwise indicated, heterocyclic rings andring systems can be attached through any available carbon or nitrogen byreplacement of a hydrogen on said carbon or nitrogen.

“Aromatic” indicates that each of the ring atoms is essentially in thesame plane and has a p-orbital perpendicular to the ring plane, and that(4n+2) it electrons, where n is a positive integer, are associated withthe ring to comply with Huickel's rule. The term “aromatic heterocyclicring system” denotes a heterocyclic ring system in which at least onering of the ring system is aromatic. The term “nonaromatic ring system”denotes a carbocyclic or heterocyclic ring system that may be fullysaturated, as well as partially or fully unsaturated, provided that noneof the rings in the ring system are aromatic. The term “four- toseven-membered nonaromatic heterocyclic ring” refers to rings containingfour to seven ring members and which do not satisfy Hickel's rule. Thisterm (as used where R⁶ and R⁷ are taken together) is not limited bycarbon atoms only and can include ring members selected from O, S(O)_(n)and NR¹³.

In the context of the present invention when an instance of Q¹, Q² or R¹comprises a phenyl or a 6-membered fully unsaturated heterocyclic ring,the ortho, meta and para positions of each ring is relative to theconnection of the ring to the remainder of Formula 1.

As noted above, Q¹, Q² and R¹ can be (among others) phenyl optionallysubstituted with one or more substituents selected from a group ofsubstituents as defined in the Summary of the Invention. An example ofphenyl optionally substituted with one to five substituents is the ringillustrated as U-57 in Exhibit A, wherein R⁸ is as defined in theSummary of the Invention for R⁸ and q is an integer from 0 to 5.

As noted above, Q¹ is, inter alia, a 5- to 6-membered fully unsaturatedheterocyclic ring or an 8- to 10-membered heteroaromatic bicyclic ringsystem, each ring or ring system containing ring members selected fromcarbon atoms and up to 4 heteroatoms independently selected from up to 2O, up to 2 S and up to 4 N atoms, wherein up to 3 carbon atom ringmembers are independently selected from C(═O) and C(═S), the sulfur atomring members are independently selected from S(═O)_(u)(═NR¹⁴)_(v), eachring or ring system optionally substituted with up to 5 substituentsindependently selected from any substituent defined in the Summary ofthe Invention for Q¹ (e.g., a Q¹ ring or ring system is optionallysubstituted with R³ on carbon ring members and cyano, C₁-C₆ alkyl, C₂-C₆alkenyl, C₂-C₆ alkynyl, C₃-C₆ cycloalkyl, C₁-C₆ alkoxy, C₂-C₆alkoxyalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-C₆alkylaminoalkyl and C₃-C₆ dialkylaminoalkyl on nitrogen atom ringmembers). Similarly, Q² is, inter alia, a 5- to 6-membered saturated,partially unsaturated or fully unsaturated heterocyclic ring or an 8- to10-membered heteroaromatic bicyclic ring system, each ring or ringsystem containing ring members selected from carbon atoms and up to 4heteroatoms independently selected from up to 2 O, up to 2 S and up to 4N atoms, wherein up to 3 carbon atom ring members are independentlyselected from C(═O) and C(═S), the sulfur atom ring members areindependently selected from S(═O)_(u)(═NR¹⁴)_(v), each ring or ringsystem optionally substituted with up to 5 substituents independentlyselected from any substituent defined in the Summary of the Inventionfor Q². As the substituents on the ring or ring system of Q¹ or Q² areoptional, 0 to 5 substituents may be present, limited only by the numberof available points of attachment. In these definitions of heterocyclicring and heteroaromatic ring system, the ring members selected from upto 2 O, up to 2 S and up to 4 N atoms are optional, provided at leastone ring member is not carbon (e.g., N, O or S). The definition ofS(═O)_(u)(═NR¹⁴)_(v) allows the up to 2 sulfur ring members, to beoxidized sulfur moieties (e.g., S(═O) or S(═O)₂) or unoxidized sulfuratoms (i.e. when u and v are both zero). The nitrogen atom ring membersmay be oxidized as N-oxides, because compounds relating to Formula 1also include N-oxide derivatives. The up to 3 carbon atom ring membersselected from C(═O) and C(═S) are in addition to the up to 4 heteroatomsselected from up to 2 O, up to 2 S and up to 4 N atoms.

Also as noted above, R¹ can be (among others) 5- or 6-memberednitrogen-containing aromatic heterocycle, which may be optionallysubstituted with one or more substituents selected from a group ofsubstituents as defined in the Summary of Invention.

When R¹ is phenyl or a 5- or 6-membered nitrogen-containing aromaticheterocycle, it may be attached to the remainder of Formula 1 throughany available carbon or nitrogen ring atom, unless otherwise described.Likewise, the ring or ring system of Q¹ or Q² may be attached to theremainder of Formula 1 through any available carbon or nitrogen ringatom, unless otherwise described.

Examples of a 5- to 6-membered fully unsaturated heterocyclic ringinclude the rings H-1 through H-39 illustrated in Exhibit 1, andexamples of an 8- to 10-membered heteroaromatic bicyclic ring systeminclude the ring systems B-1 through B-39 illustrated in Exhibit 2. InExhibits 1 and 2 the variable R^(a) is any substituent as defined in theSummary of the Invention for Q¹, Q² or R¹ (e.g., a Q¹ ring or ringsystem is optionally substituted with R³ on carbon ring members andcyano, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆ cycloalkyl,C₁-C₆ alkoxy, C₂-C₆ alkoxyalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆ alkylaminoalkyl and C₃-C₆ dialkylaminoalkyl onnitrogen atom ring members) and r is an integer from 0 to 5 for Q¹ andQ² or from 0 to 3 for R¹, limited by the number of available positionson each depicted ring or ring system.

Exhibit 1

Exhibit 2

Examples of a saturated or partially unsaturated 5- to 6-membered fullyunsaturated heterocyclic ring include the rings P-1 through P-40illustrated in Exhibit 3. In Exhibit 3 the variable R^(a) is anysubstituent as defined in the Summary of the Invention for Q² (e.g., aQ² ring is optionally substituted with R³ on carbon ring members andcyano, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆ cycloalkyl,C₁-C₆ alkoxy, C₂-C₆ alkoxyalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆ alkylaminoalkyl and C₃-C₆ dialkylaminoalkyl onnitrogen atom ring members) and r is an integer from 0 to 5, limited bythe number of available positions on each depicted ring or ring system.

Exhibit 3

Examples of a 5- or 6-membered nitrogen-containing heterocycleoptionally substituted with from one or more substituents of particularnote for Q¹, Q² and R¹ include the rings U-1 through U-56 illustrated inExhibit A wherein R^(a) is any substituent as defined in the Summary ofthe Invention for Q¹ Q² and R¹, respectively (i.e. for Q¹ and Q²: R³ oncarbon atom ring members, and the recited list of possible substituentson nitrogen atom ring members; and for R¹, R^(9a) on carbon ring membersand R^(9b) on nitrogen ring members) and r is an integer ranging from 0to 4 for Q¹ and Q² and from 0 to 3 for R¹, limited by the number ofavailable positions on each U group. Note that some U groups can only besubstituted with less than 4 R^(a) groups (e.g., U-4 through U-43 andU-47 through U-56). As U-24, U-25, U-31, U-32, U-33, U-34, U-35, U-36,U-37 and U-38 have only one available position, for these U groups, r islimited to the integers 0 or 1, and r being 0 means that the U group isunsubstituted and a hydrogen is present at the position indicated by(R^(a))_(r).

Exhibit A

Although R^(a) groups are shown in the structures H-1 through H-39, B-1through B-39, P-1 through P-40, and U-1 through U-57 in Exhibits 1through 3 and Exhibit A, it is noted that they do not need to be presentsince they are optional substituents. The nitrogen atoms that requiresubstitution to fill their valence are substituted with H or R^(a). Notethat when the attachment point between (R^(a))_(r) and the H, B, P or Ugroup in Exhibits 1 through 3 and Exhibit A is illustrated as floating,(R^(a))_(r) can be attached to any available carbon atom or nitrogenatom of the H, B, P or U group. Note that when the attachment point onthe H, B or P group in Exhibits 1 through 3 is illustrated as floating,the H, B or P group can be attached to the remainder of Formula 1through any available carbon or nitrogen of the H, B or P group byreplacement of a hydrogen atom. Of note are alternative depictions ofthe chemical structures shown in Exhibits 1 through 3 and Exhibit A inwhich the “R^(a)” variable substituent is replaced by “R^(v)”, whereinthe “v” superscript in “R^(v)” does not refer to the subscript variable“v” defined in the Summary of the Invention but instead differentiates“R^(v)” from other substituent variables beginning with “R”.

Examples of where R⁶ and R⁷ are taken together to form a four- toseven-membered nonaromatic heterocyclic ring include the rings G-1through G-28 as illustrated in Exhibit 4. Note that when R⁶ and R⁷ aretaken together to form a ring comprising a ring selected from G-25through G-28, G² is selected from O, S(O)_(n) or NR¹³. Note that when G²is N, the nitrogen atom can complete its valence by substitution witheither H or the substituents corresponding to R¹³ as defined in theSummary of Invention.

Exhibit 4

A wide variety of synthetic methods are known in the art to enablepreparation of aromatic and nonaromatic heterocyclic rings and ringsystems; for extensive reviews see the eight volume set of ComprehensiveHeterocyclic Chemistry, A. R. Katritzky and C. W. Rees editors-in-chief,Pergamon Press, Oxford, 1984 and the twelve volume set of ComprehensiveHeterocyclic Chemistry II, A. R. Katritzky, C. W. Rees and E. F. V.Scriven editors-in-chief, Pergamon Press, Oxford, 1996.

Compounds of this invention can exist as one or more stereoisomers. Thevarious stereoisomers include enantiomers, diastereomers, atropisomersand geometric isomers. One skilled in the art will appreciate that onestereoisomer may be more active and/or may exhibit beneficial effectswhen enriched relative to the other stereoisomer(s) or when separatedfrom the other stereoisomer(s). Additionally, the skilled artisan knowshow to separate, enrich, and/or to selectively prepare saidstereoisomers. The compounds of the invention may be present as amixture of stereoisomers, individual stereoisomers or as an opticallyactive form.

One skilled in the art will appreciate that not all nitrogen-containingheterocycles can form N-oxides since the nitrogen requires an availablelone pair for oxidation to the oxide; one skilled in the art willrecognize those nitrogen-containing heterocycles which can formN-oxides. One skilled in the art will also recognize that tertiaryamines can form N-oxides. Synthetic methods for the preparation ofN-oxides of heterocycles and tertiary amines are very well known by oneskilled in the art including the oxidation of heterocycles and tertiaryamines with peroxy acids such as peracetic and m-chloroperbenzoic acid(MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butylhydroperoxide, sodium perborate, and dioxiranes such asdimethyldioxirane. These methods for the preparation of N-oxides havebeen extensively described and reviewed in the literature, see forexample: T. L. Gilchrist in Comprehensive Organic Synthesis, vol. 7, pp748-750, S. V. Ley, Ed., Pergamon Press; M. Tisler and B. Stanovnik inComprehensive Heterocyclic Chemistry, vol. 3, pp 18-20, A. J. Boultonand A. McKillop, Eds., Pergamon Press; M. R. Grimmett and B. R. T. Keenein Advances in Heterocyclic Chemistry, vol. 43, pp 149-161, A. R.Katritzky, Ed., Academic Press; M. Tisler and B. Stanovnik in Advancesin Heterocyclic Chemistry, vol. 9, pp 285-291, A. R. Katritzky and A. J.Boulton, Eds., Academic Press; and G. W. H. Cheeseman and E. S. G.Werstiuk in Advances in Heterocyclic Chemistry, vol. 22, pp 390-392, A.R. Katritzky and A. J. Boulton, Eds., Academic Press.

One skilled in the art recognizes that some of the compounds disclosedherein can exist in equilibrium with one or more of their respectivetautomeric counterparts. Unless otherwise indicated, reference to acompound by one tautomer description is to be considered to include alltautomers. For example, reference to the tautomeric form depicted byFormula 21 also includes the tautomic form depicted by Formula 22.

One skilled in the art recognizes that because in the environment andunder physiological conditions salts of chemical compounds are inequilibrium with their corresponding nonsalt forms, salts share thebiological utility of the nonsalt forms. Thus a wide variety of salts ofthe compounds of Formula 1 are useful for control of plant diseasescaused by fungal plant pathogens (i.e. are agriculturally suitable). Thesalts of the compounds of Formula 1 include acid-addition salts withinorganic or organic acids such as hydrobromic, hydrochloric, nitric,phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic,oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valericacids.

Compounds selected from Formula 1, geometric and stereoisomers,tautomers, N-oxides, and salts thereof, typically exist in more than oneform, and Formula 1 thus includes all crystalline and non-crystallineforms of the compounds that Formula 1 represents. Non-crystalline formsinclude embodiments which are solids such as waxes and gums as well asembodiments which are liquids such as solutions and melts. Crystallineforms include embodiments which represent essentially a single crystaltype and embodiments which represent a mixture of polymorphs (i.e.different crystalline types). The term “polymorph” refers to aparticular crystalline form of a chemical compound that can crystallizein different crystalline forms, these forms having differentarrangements and/or conformations of the molecules in the crystallattice. Although polymorphs can have the same chemical composition,they can also differ in composition due the presence or absence ofco-crystallized water or other molecules, which can be weakly orstrongly bound in the lattice. Polymorphs can differ in such chemical,physical and biological properties as crystal shape, density, hardness,color, chemical stability, melting point, hygroscopicity,suspensibility, dissolution rate and biological availability. Oneskilled in the art will appreciate that a polymorph of a compoundrepresented by Formula 1 can exhibit beneficial effects (e.g.,suitability for preparation of useful formulations, improved biologicalperformance) relative to another polymorph or a mixture of polymorphs ofthe same compound represented by Formula 1. Preparation and isolation ofa particular polymorph of a compound represented by Formula 1 can beachieved by methods known to those skilled in the art including, forexample, crystallization using selected solvents and temperatures.

Embodiments of the present invention as described in the Summary of theInvention include (where Formula 1 as used in the following Embodimentsincludes N-oxides and salts, geometric isomers, stereoisomers andatropisomers thereof):

Embodiment 1

A compound of Formula 1 wherein X is O, S(O)_(m), NR⁴, CR¹⁵R¹⁶ or C(═O).

Embodiment 2

A compound of Formula 1 wherein X is O, S(O)_(m), NR⁴ or CR¹⁵R¹⁶.

Embodiment 3

A compound of Formula 1 wherein X is O, NR⁴, CR¹⁵R¹⁶ or C(═O).

Embodiment 4

A compound of Formula 1 wherein X is O, NR⁴ or CR¹⁵R¹⁶.

Embodiment 5

A compound of Formula 1 wherein X is O, S(O)_(m) or NR⁴.

Embodiment 6

A compound of Formula 1 wherein X is O or S(O)_(m).

Embodiment 7

A compound of Formula 1 wherein X is O.

Embodiment 8

A compound of Formula 1 wherein X is NR⁴.

Embodiment 9

A compound of Formula 1 wherein X is O or NR⁴.

Embodiment 10

A compound of Formula 1 wherein X is CR¹⁵R¹⁶, C(═O) or C(═S).

Embodiment 11

A compound of Formula 1 or any one of Embodiments 1 through 10 whereinwhen Q¹ is a six-membered ring (e.g., phenyl, pyridinyl, pyrimidinyl,pyrazinyl or pyridazinyl) and an R³ substituent is located at a metaposition (relative to the connection of the Q¹ ring to the remainder ofFormula 1), then said R³ substituent is selected from F, Cl, Br andcyano (—CN).

Embodiment 11a

A compound of Formula 1 or any one of Embodiments 1 through 11 whereinwhen Q¹ is a six-membered ring and an R³ substituent is located at ameta position (relative to the connection of the Q¹ ring to theremainder of Formula 1), then said R³ substituent is F.

Embodiment 12

A compound of Formula 1 or any one of Embodiments 1 through 11a whereinwhen Q¹ is a six-membered ring (e.g., phenyl, pyridinyl, pyrimidinyl,pyrazinyl or pyridazinyl) substituted with only one R³ substituent, thensaid R³ substituent is attached at an ortho position (relative to theconnection of the Q¹ ring to the remainder of Formula 1).

Embodiment 13

A compound of Formula 1 or any one of Embodiments 1 through 12 whereinQ¹ is phenyl, thienyl, pyridinyl, pyridazinyl, pyrazinyl, pyrimidinyl,naphthalenyl, quinolinyl, isoquinolinyl or quinoxalinyl, each optionallysubstituted with up to 5 substituents independently selected from R³.

Embodiment 14

A compound of Embodiment 13 wherein Q¹ is phenyl, thienyl, pyridinyl,pyridazinyl, pyrazinyl or pyrimidinyl, each optionally substituted withup to 5 substituents independently selected from R³.

Embodiment 15

A compound of Embodiment 14 wherein Q¹ is phenyl, pyridinyl,pyrimidinyl, pyrazinyl or pyridazinyl, each substituted with from 1 to 4substituents independently selected from R³.

Embodiment 16

A compound of Embodiment 15 wherein Q¹ is phenyl, pyridinyl,pyrimidinyl, pyrazinyl or pyridazinyl, each substituted with 1, 2 or 3substituents independently selected from R³.

Embodiment 17

A compound of Embodiment 16 wherein the substituents are located at theortho and/or para positions (relative to the connection of the Q¹ ringto the remainder of Formula 1) of the phenyl, pyridinyl, pyrimidinyl,pyrazinyl or pyridazinyl of Q¹.

Embodiment 18

A compound of Embodiment 16 or 17 wherein Q¹ is phenyl or pyridinyl,each substituted with 1, 2 or 3 substituents independently selected fromR³.

Embodiment 19

A compound of Embodiment 18 wherein Q¹ is phenyl or pyridinyl, eachsubstituted with 2 or 3 substituents independently selected from R³.

Embodiment 20

A compound of Embodiment 19 wherein Q¹ is phenyl substituted at the 2-,4- and 6-positions with substituents independently selected from R³; orphenyl substituted at the 2- and 4-positions with substituentsindependently selected from R³; or phenyl substituted at the 2- and6-positions with substituents independently selected from R³.

Embodiment 21

A compound of Embodiment 20 wherein Q¹ is phenyl substituted at the 2-,4- and 6-positions with substituents independently selected from R³; orphenyl substituted at the 2- and 4-positions with substituentsindependently selected from R³.

Embodiment 22

A compound of Embodiment 21 wherein Q¹ is phenyl substituted at the 2-,4- and 6-positions with substituents independently selected from R³.

Embodiment 23

A compound of Embodiment 21 wherein Q¹ is phenyl substituted at the 2-and 4-positions with substituents independently selected from R³.

Embodiment 24

A compound of Embodiment 21 wherein Q¹ is phenyl substituted at the 2-and 6-positions with substituents independently selected from R³.

Embodiment 25

A compound of Embodiment 18 wherein Q¹ is pyridinyl substituted with 1,2 or 3 substituents independently selected from R³.

Embodiment 26

A compound of Embodiment 25 wherein Q¹ is pyridinyl substituted with 1or 2 substituents independently selected from R³.

Embodiment 27

A compound of Embodiment 26 wherein Q¹ is pyridinyl substituted with 1substituent independently selected from R³.

Embodiment 28

A compound of Formula 1 or any one of Embodiments 1 through 27 whereinwhen Q² is a six-membered ring (e.g., phenyl, pyridinyl, pyrimidinyl,pyrazinyl or pyridazinyl) and an R³ substituent is located at a metaposition (relative to the connection of the Q² ring to the remainder ofFormula 1), then said R³ substituent is selected from F, Cl, Br andcyano (—CN).

Embodiment 29

A compound of Formula 1 or any one of Embodiments 1 through 28 whereinwhen Q² is a six-membered ring and an R³ substituent is located at ameta position (relative to the connection of the Q² ring to theremainder of Formula 1), then said R³ substituent is F.

Embodiment 30

A compound of Formula 1 or any one of Embodiments 1 through 29 whereinwhen Q² is a six-membered ring (e.g., phenyl, pyridinyl, pyrimidinyl,pyrazinyl or pyridazinyl) substituted with only one R³ substituent, thensaid R³ substituent is attached at an ortho position (relative to theconnection of the Q² ring to the remainder of Formula 1).

Embodiment 31

A compound of Formula 1 or any one of Embodiments 1 through 30 whereinQ² is phenyl, thienyl, pyridinyl, pyridazinyl, pyrazinyl, pyrimidinyl,naphthalenyl, quinolinyl, isoquinolinyl or quinoxalinyl, each optionallysubstituted with up to 5 substituents independently selected from R³.

Embodiment 32

A compound of Embodiment 31 wherein Q² is phenyl, thienyl, pyridinyl,pyridazinyl, pyrazinyl or pyrimidinyl, each optionally substituted withup to 5 substituents independently selected from R³.

Embodiment 33

A compound of Embodiment 32 wherein Q² is phenyl, pyridinyl,pyrimidinyl, pyrazinyl or pyridazinyl, each substituted with from 1 to 4substituents independently selected from R³.

Embodiment 34

A compound of any one of Embodiments 31 through 33 wherein Q² is phenyl,pyridinyl, pyrimidinyl, pyrazinyl or pyridazinyl, each substituted with1, 2 or 3 substituents independently selected from R³.

Embodiment 35

A compound of Embodiment 34 wherein the substituents are located at theortho and/or para positions (relative to the connection of the Q² ringto the remainder of Formula 1) of the phenyl, pyridinyl, pyrimidinyl,pyrazinyl or pyridazinyl of Q².

Embodiment 36

A compound of any one of Embodiments 34 or 35 wherein Q² is phenyl orpyridinyl, each substituted with 1, 2 or 3 substituents independentlyselected from R³.

Embodiment 37

A compound of Embodiment 36 wherein Q² is phenyl substituted with 1, 2or 3 substituents independently selected from R³.

Embodiment 38

A compound of Embodiment 37 wherein Q² is phenyl substituted at the 2-,4- and 6-positions with substituents independently selected from R³; orphenyl substituted at the 2- and 4-positions with substituentsindependently selected from R³; or phenyl substituted at the 2- and6-positions with substituents independently selected from R³.

Embodiment 39

A compound of Embodiment 38 wherein Q² is phenyl substituted at the 2-,4- and 6-positions with substituents independently selected from R³.

Embodiment 40

A compound of Embodiment 38 wherein Q² is phenyl substituted at the 2-and 4-positions with substituents independently selected from R³.

Embodiment 41

A compound of Embodiment 38 wherein Q² is phenyl substituted at the 2-and 6-positions with substituents independently selected from R³.

Embodiment 42

A compound of Embodiment 36 wherein Q² is pyridinyl substituted with 1,2 or 3 substituents independently selected from R³.

Embodiment 43

A compound of Embodiment 42 wherein Q² is pyridinyl substituted with 1or 2 substituents independently selected from R³.

Embodiment 44

A compound of Embodiment 43 wherein Q² is pyridinyl substituted with 1substituent selected from R³.

Embodiment 45

A compound of Formula 1 or any one of Embodiments 1 through 44 whereinat least one of Q¹ and Q² is phenyl optionally substituted with R³(e.g., optionally substituted with up to 5 substituents independentlyselected from R³).

Embodiment 46

A compound of Embodiment 45 wherein at least one of Q¹ and Q² is phenylsubstituted with 2, 3 or 4 substituents independently selected from R³.

Embodiment 47

A compound of Embodiment 46 wherein at least one Q¹ and Q² is phenylsubstituted with 2 or 3 substituents independently selected from R³.

Embodiment 48

A compound of Embodiment 47 wherein each of Q¹ and Q² is phenylsubstituted with 2 or 3 substituents independently selected from R³.

Embodiment 49

A compound of Formula 1 or any one of Embodiments 1 through 48 whereinR¹ is H, halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl, CO₂R⁵, C(O)NR⁶R⁷, cyano,C₁-C₆ alkoxy, C₁-C₆ haloalkoxy or C₂-C₅ alkoxyalkyl; or R¹ is a five- orsix-membered nitrogen-containing aromatic heterocycle optionallysubstituted with up to 3 substituents independently selected from R^(9a)on carbon atom ring members and R^(9b) on nitrogen atom ring members.

Embodiment 50

A compound of Embodiment 49 wherein R¹ is H, halogen, C₁-C₆ alkyl, C₁-C₆haloalkyl, cyano, C₁-C₆ alkoxy or C₁-C₆ haloalkoxy; or R¹ is pyridinyl,pyrimidinyl, pyrazolyl or oxazolyl, each optionally substituted with upto 3 substituents independently selected from R^(9a) on carbon atom ringmembers and R^(9b) on nitrogen atom ring members.

Embodiment 51

A compound of Embodiment 50 wherein R¹ is H, halogen, C₁-C₆ alkyl, C₁-C₆haloalkyl, CO₂R⁵, C(O)NR⁶R⁷, cyano, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy orC₂-C₅ alkoxyalkyl.

Embodiment 52

A compound of Embodiment 51 wherein R¹ is H, halogen, C₁-C₆ alkyl, C₁-C₆haloalkyl, C(O)NR⁶R⁷, cyano, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy or C₂-C₅alkoxyalkyl.

Embodiment 53

A compound of Embodiment 52 wherein R¹ is H, halogen, C₁-C₆ alkyl, C₁-C₆haloalkyl, cyano, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy or C₂-C₅ alkoxyalkyl.

Embodiment 54

A compound of Embodiment 53 wherein R¹ is H, halogen or C₁-C₆ alkyl.

Embodiment 55

A compound of Embodiment 54 wherein R¹ is H or CH₃.

Embodiment 56

A compound of Embodiment 55 wherein R¹ is H.

Embodiment 57

A compound of Formula 1 or any one of Embodiments 1 through 56 whereinR¹ is other than an optionally substituted phenyl or an optionallysubstituted five- or six-membered nitrogen-containing aromaticheterocycle.

Embodiment 58

A compound of Formula 1 or any one of Embodiments 1 through 50 whereinR¹ is other than H, halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₄alkenyl, C₂-C₄ alkynyl, C₃-C₇ cycloalkyl, CO₂R⁵, C(O)NR⁶R⁷, cyano, C₁-C₆alkoxy, C₁-C₆ haloalkoxy or C₂-C₅ alkoxyalkyl.

Embodiment 59

A compound of Formula 1 or any one of Embodiments 1 through 58 whereinR^(1a) is H.

Embodiment 60

A compound of Formula 1 or any one of Embodiments 1 through 59 whereinR² is CH₃, CH₂CH₃, halogen, cyano, cyanomethyl, monohalomethyl,hydroxymethyl, methoxy or methylthio; or cyclopropyl optionallysubstituted with up to 2 substituents independently selected fromhalogen and methyl.

Embodiment 61

A compound of Embodiment 60 wherein R² is CH₃, CH₂CH₃, Cl, Br or I.

Embodiment 62

A compound of Embodiment 61 wherein R² is CH₃, CH₂CH₃, Cl or Br.

Embodiment 63

A compound of Embodiment 62 wherein R² is CH₃, Cl or Br.

Embodiment 64

A compound of Embodiment 63 wherein R² is CH₃ or Cl.

Embodiment 65

A compound of Embodiment 64 wherein R² is CH₃.

Embodiment 66

A compound of Embodiment 62 wherein R² is Cl or Br.

Embodiment 67

A compound of Embodiment 66 wherein R² is Cl.

Embodiment 68

A compound of Formula 1 or any one of Embodiments 1 through 67 whereinR⁵ is H or C₁-C₆ alkyl.

Embodiment 69

A compound of Embodiment 68 wherein R⁵ is H, CH₃ or CH₂CH₃.

Embodiment 70

A compound of Embodiment 68 wherein R⁵ is C₁-C₆ alkyl.

Embodiment 71

A compound of Embodiment 69 or 70 wherein R⁵ is CH₃ or CH₂CH₃.

Embodiment 72

A compound of Formula 1 or any one of Embodiments 1 through 71 whereinwhen R⁶ is separate (i.e. not taken together with R⁷ to form a ring),then R⁶ is H or C₁-C₆ alkyl.

Embodiment 73

A compound of Embodiment 72 wherein R⁶ is H.

Embodiment 74

A compound of Formula 1 or any one of Embodiments 1 through 73 whereinwhen R⁷ is separate (i.e. not taken together with R⁶ to form a ring),then R⁷ is H, C₁-C₆ alkyl, C₁-C₆ haloalkyl or C₄-C₈ alkylcycloalkyl.

Embodiment 75

A compound of Embodiment 74 wherein R⁷ is H or C₁-C₆ alkyl.

Embodiment 76

A compound of Embodiment 75 wherein R⁷ is H.

Embodiment 77

A compound of Formula 1 or any one Embodiments 1 through 76 wherein whenR⁶ and R⁷ are taken together with the nitrogen atom to which they areconnected to form a nonaromatic heterocyclic ring, the ring containsring members, in addition to the connecting nitrogen atom, selected fromcarbon atoms and up to one ring member selected from O and NR¹³.

Embodiment 78

A compound of Embodiment 77 wherein when R⁶ and R⁷ are taken togetherwith the nitrogen atom to which they are connected to form a nonaromaticheterocyclic ring, the ring is six-membered and contains one ring memberselected from O and NR¹³ in addition to the connecting nitrogen atom andring members selected from carbon atoms.

Embodiment 79

A compound of Embodiment 77 wherein R⁶ and R⁷ are taken together withthe nitrogen atom to which they are connected to form a piperidine ring.

Embodiment 80

A compound of Embodiment 78 wherein R⁶ and R⁷ are taken together withthe nitrogen atom to which they are connected to form a piperazine ormorpholine ring.

Embodiment 81

A compound of Formula 1 or any one of Embodiments 1 through 80 whereineach R⁸ is independently selected from halogen, C₁-C₂ alkyl, C₁-C₂haloalkyl, C₁-C₂ alkoxy, C₁-C₂ haloalkoxy, cyano and nitro.

Embodiment 82

A compound of Embodiment 81 wherein each R⁸ is independently selectedfrom halogen, C₁-C₂ alkyl, C₁-C₂ alkoxy, cyano and nitro.

Embodiment 83

A compound of Embodiment 82 wherein each R⁸ is independently Cl or F.

Embodiment 84

A compound of Formula 1 or any one of Embodiments 1 through 83 whereineach R^(9a) is independently selected from halogen, C₁-C₂ alkyl, C₁-C₂haloalkyl, C₁-C₂ alkoxy, C₁-C₂ haloalkoxy, cyano and nitro.

Embodiment 85

A compound of Embodiment 84 wherein each R^(9a) is independentlyselected from halogen, C₁-C₂ alkyl, C₁-C₂ alkoxy, cyano and nitro.

Embodiment 86

A compound of Embodiment 85 wherein each R^(9a) is independentlyselected from Cl, F, CH₃, —OCH₃ and cyano.

Embodiment 87

A compound of Embodiment 86 wherein each R^(9a) is independently Cl orF.

Embodiment 88

A compound of Formula 1 or any one of Embodiments 1 through 87 whereineach R^(9b) is independently C₁-C₂ alkyl.

Embodiment 89

A compound of Formula 1 or any one of Embodiments 1 through 88 whereineach R³ is independently selected from halogen, cyano, nitro, amino,methylamino, dimethylamino, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₃ alkoxy,C₁-C₃ haloalkoxy, C₁-C₃ alkylthio, C₁-C₃ haloalkylthio, C₁-C₃alkylsulfinyl, C₁-C₃ haloalkylsulfinyl, C₁-C₃ alkylsulfonyl, C₁-C₃haloalkylsulfonyl, C₃-C₄ cycloalkyl, C(═S)NH₂ and —U—V-T.

Embodiment 90

A compound of Embodiment 89 wherein each R³ is independently selectedfrom halogen, cyano, nitro, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₃ alkoxy,C₁-C₃ haloalkoxy and —U—V-T.

Embodiment 91

A compound of Embodiment 90 wherein each R³ is independently selectedfrom F, Cl, Br, cyano, nitro, CH₃, CF₃, —OCH₃, —OCHF₂ and —U—V-T.

Embodiment 92

A compound of Formula 1 or any one of Embodiments 1 through 91 whereinat least one R³ substituent on the ring or ring system of Q¹ or Q² is—U—V-T.

Embodiment 93

A compound of Formula 1 or any one of Embodiments 1 through 91 whereineach R³ is other than —U—V-T.

Embodiment 94

A compound of Embodiment 89 wherein each R³ is independently selectedfrom halogen, cyano, nitro, amino, methylamino, dimethylamino, C₁-C₄alkyl, C₁-C₄ haloalkyl, C₁-C₃ alkoxy, C₁-C₃ haloalkoxy, C₁-C₃ alkylthio,C₁-C₃ haloalkylthio, C₁-C₃ alkylsulfinyl, C₁-C₃ haloalkylsulfinyl, C₁-C₃alkylsulfonyl, C₁-C₃ haloalkylsulfonyl and C₃-C₄ cycloalkyl.

Embodiment 95

A compound of Embodiment 94 wherein each R³ is independently selectedfrom halogen, cyano, nitro, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₃ alkoxyand C₁-C₃ haloalkoxy.

Embodiment 96

A compound of Embodiment 95 wherein each R³ is independently selectedfrom halogen, cyano, C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₁-C₃ alkoxy andC₁-C₃ haloalkoxy.

Embodiment 97

A compound of Embodiment 96 wherein each R³ is independently selectedfrom F, Cl, Br, cyano, C₁-C₂ alkyl, C₁-C₂ haloalkyl, C₁-C₂ alkoxy andC₁-C₂ haloalkoxy.

Embodiment 98

A compound of Embodiment 97 wherein each R³ is independently selectedfrom F, Cl, Br, cyano, methyl, C₁-C₂ alkoxy and fluoromethoxy.

Embodiment 99

A compound of Embodiment 98 wherein each R³ is independently selectedfrom F, Cl, cyano, methyl, C₁-C₂ alkoxy and fluoromethoxy.

Embodiment 100

A compound of Embodiment 95 wherein each R³ is independently selectedfrom F, Cl, Br, cyano, nitro, CH₃, CF₃, —OCH₃ and —OCHF₂.

Embodiment 101

A compound of any one of Embodiments 89 through 98 or 100 wherein eachR³ is independently selected from F, Cl, Br, cyano and methoxy.

Embodiment 102

A compound of Embodiment 101 wherein each R³ is independently selectedfrom F, Cl, Br and cyano.

Embodiment 103

A compound of Embodiment 101 wherein each R³ is independently selectedfrom F, Cl, cyano and —OCH₃.

Embodiment 104

A compound of Formula 1 or any one of Embodiments 1 through 92 whereineach U is independently O or NR²².

Embodiment 105

A compound of Embodiment 104 wherein each U is independently O or NH.

Embodiment 106

A compound of Formula 1 or any one of Embodiments 1 through 92 and 104through 105 wherein each V is C₂-C₄ alkylene.

Embodiment 107

A compound of Formula 1 or any one of Embodiments 1 through 92 and 104through 106 wherein each T is independently NR^(23a)R^(23b) or OR²⁴.

Embodiment 108

A compound of Formula 1 or any one of Embodiments 1 through 92 and 104through 107 wherein each R^(23a) and R^(23b) is independently H, C₁-C₆alkyl or C₁-C₆ haloalkyl.

Embodiment 109

A compound of Formula 1 or any one of Embodiments 1 through 92 and 104through 108 wherein each R²⁴ is independently H, C₁-C₆ alkyl or C₁-C₆haloalkyl.

Embodiment 110

A compound of Formula 1 or any one of Embodiments 1 through 109 whereinwhen an R³ substituent attached to phenyl, pyridinyl, pyrimidinyl,pyrazinyl or pyridazinyl of Q¹ or Q² is other than F, Cl, Br, cyano,methyl, C₁-C₂ alkoxy and fluoromethoxy, then said R³ substituent isattached at the para position (of the phenyl, pyridinyl, pyrimidinyl,pyrazinyl or pyridazinyl ring).

Embodiment 111

A compound of Formula 1 or any one of Embodiments 1 through 110 whereinR⁴ is H, formyl, C₃-C₇ cycloalkyl or —SR¹⁰; or C₁-C₆ alkyl or C₁-C₆haloalkyl, each optionally substituted with up to 2 R¹².

Embodiment 112

A compound of Embodiment 111 wherein R⁴ is H, formyl, C₃-C₇ cycloalkylor —SR¹⁰; or C₁-C₆ alkyl substituted with one R¹².

Embodiment 113

A compound of Embodiment 112 wherein R⁴ is H, formyl, —CH₂OCH₃,cyclopropyl, —SCH₃, —SCF₃ or —CH₂CN.

Embodiment 114

A compound of Embodiment 113 wherein R⁴ is H, formyl, cyclopropyl or—CH₂CN.

Embodiment 115

A compound of Embodiment 113 wherein R⁴ is H, formyl, —CH₂OCH₃,cyclopropyl, —SCH₃ or —SCF₃.

Embodiment 116

A compound of Embodiment 115 wherein R⁴ is H, formyl or cyclopropyl.

Embodiment 117

A compound of Embodiment 114 or 116 wherein R⁴ is H.

Embodiment 118

A compound of Formula 1 or any one of Embodiments 1 through 117 whereinR¹³ is H or CH₃.

Embodiment 119

A compound of Embodiment 118 wherein R¹³ is CH₃.

Embodiment 120

A compound of Formula 1 or any one of Embodiments 1 through 119 whereineach R¹² is independently C₃-C₇ cycloalkyl, C₁-C₄ alkoxy or cyano.

Embodiment 121

A compound of Embodiment 120 wherein each R¹² is independentlycyclopropyl, —OCH₃ or cyano.

Embodiment 122

A compound of Embodiment 120 wherein each R¹² is independently C₃-C₇cycloalkyl or C₁-C₄ alkoxy.

Embodiment 123

A compound of Embodiment 122 wherein each R¹² is independentlycyclopropyl or —OCH₃.

Embodiment 124

A compound of Formula 1 or any one of Embodiments 1 through 123 whereinR¹⁰ is CH₃, CH₂CH₃, CF₃ or CF₂CF₃.

Embodiment 125

A compound of Embodiment 124 wherein R¹⁰ is CH₃.

Embodiment 126

A compound of Formula 1 or any one of Embodiments 1 through 125 whereinR¹¹ is C₁-C₆ alkyl, C₁-C₆ alkoxy or C₁-C₆ alkylthio.

Embodiment 127

A compound of Embodiment 126 wherein R¹¹ is CH₃, CH₂CH₃, —OCH₃,—OCH₂CH₃, —SCH₃ or —SCH₂CH₃.

Embodiment 128

A compound of Embodiment 127 wherein R¹¹ is CH₃, —OCH₃ or —SCH₃.

Embodiment 129

A compound of Formula 1 or any one of Embodiments 1 through 128 whereinR¹⁵ is H or CH₃.

Embodiment 130

A compound of Embodiment 129 wherein R¹⁵ is H.

Embodiment 131

A compound of Formula 1 or any one of Embodiments 1 through 130 whereinR¹⁶ is CH₃ or OR¹⁸.

Embodiment 132

A compound of Embodiment 131 wherein R¹⁶ is OR¹⁸.

Embodiment 133

A compound of Formula 1 or any one of Embodiments 1 through 132 whereinR¹⁸ is H.

Embodiment 134

A compound of Formula 1 or any one of Embodiments 1 through 133 whereinW is O.

Embodiment 135

A compound of Formula 1 or any one of Embodiments 1 through 134 whereinM⁺ is a cation selected from sodium, potassium and lithium ions.

Embodiment 136

A compound of Embodiment 135 wherein M⁺ is a cation selected from sodiumand potassium ions.

Embodiment 137

A compound of Embodiment 136 wherein M⁺ is a sodium ion.

Embodiment 138

A compound of Formula 1 or any one of Embodiments 1 through 137 whereinm is 0.

Embodiment 139

A compound of Formula 1 or any one of Embodiments 1 through 138 whereinn is 0.

Embodiments of this invention, including Embodiments 1-139 above as wellas any other embodiments described herein, can be combined in anymanner, and the descriptions of variables in the embodiments pertain notonly to the compounds of Formula 1 but also to the starting compoundsand intermediate compounds (e.g. compounds of Formula 2) useful forpreparing the compounds of Formula 1. In addition, embodiments of thisinvention, including Embodiments 1-139 above as well as any otherembodiments described herein, and any combination thereof, pertain tothe compositions and methods of the present invention.

Combinations of Embodiments 1-139 are illustrated by:

Embodiment A

A compound of Formula 1 wherein

-   -   Q¹ is phenyl, pyridinyl, pyrimidinyl, pyrazinyl or pyridazinyl,        each substituted with from 1 to 4 substituents independently        selected from R³; provided that when an R³ substituent is        located at a meta position, then said R³ substituent is selected        from F, Cl, Br and cyano;    -   Q² is phenyl, pyridinyl, pyrimidinyl, pyrazinyl or pyridazinyl,        each substituted with 1, 2 or 3 substituents independently        selected from R³, provided that when an R³ substituent is        located at a meta position, then said R³ substituent is selected        from F, Cl, Br and cyano;    -   X is O, NR⁴, C(═O) or CR¹⁵R¹⁶;    -   R¹ is H, halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl, CO₂R⁵,        C(O)NR⁶R⁷, cyano, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy or C₂-C₅        alkoxyalkyl;    -   R^(1a) is H;    -   R² is CH₃, CH₂CH₃, Cl or Br;    -   each R³ is independently selected from halogen, cyano, nitro,        amino, methylamino, dimethylamino, C₁-C₄ alkyl, C₁-C₄ haloalkyl,        C₁-C₃ alkoxy, C₁-C₃ haloalkoxy C₁-C₃ alkylthio, C₁-C₃        haloalkylthio, C₁-C₃ alkylsulfinyl, C₁-C₃ haloalkylsulfinyl,        C₁-C₃ alkylsulfonyl, C₁-C₃ haloalkylsulfonyl, C₃-C₄ cycloalkyl,        C(═S)NH₂ and —U—V-T;    -   R⁴ is H, formyl, C₃-C₇ cycloalkyl or —SR¹⁰; or C₁-C₆ alkyl or        C₁-C₆ haloalkyl, each optionally substituted with up to 2 R¹²;    -   R⁵ is C₁-C₆ alkyl;    -   R⁶ is H or C₁-C₆ alkyl;    -   R⁷ is H, C₁-C₆ alkyl, C₁-C₆ haloalkyl or C₄-C₈ alkylcycloalkyl;        or    -   R⁶ and R⁷ are taken together with the nitrogen atom to which        they are connected to form a four- to seven-membered nonaromatic        heterocyclic ring containing ring members, in addition to the        connecting nitrogen atom, selected from carbon atoms and up to        one ring member selected from O and NR¹³;    -   each R¹² is independently C₃-C₇ cycloalkyl, C₁-C₄ alkoxy or        cyano;    -   R¹³ is H or CH₃;    -   R¹⁵ is H or CH₃; and    -   R¹⁶ is OR¹⁸.

Embodiment B

A compound of Embodiment A wherein

-   -   Q¹ is phenyl or pyridinyl, each substituted with 1, 2 or 3        substituents independently selected from R³;    -   Q² is phenyl or pyridinyl, each substituted with 1, 2 or 3        substituents independently selected from R³;    -   R¹ is H, halogen or C₁-C₆ alkyl;    -   R² is CH₃, Cl or Br;    -   each R³ is independently selected from halogen, cyano, nitro,        C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₃ alkoxy, C₁-C₃ haloalkoxy and        —U—V-T;    -   R⁴ is H, formyl, C₃-C₇ cycloalkyl or —SR¹⁰; or C₁-C₆ alkyl        substituted with one R¹²;    -   each R¹² is independently cyclopropyl, —OCH₃ or cyano;    -   R¹⁵ is H;    -   each U is independently O or NH;    -   each V is C₂-C₄ alkylene;    -   each T is independently NR^(23a)R^(23b) or OR²⁴;    -   each R^(23a) and R^(23b) is independently H, C₁-C₆ alkyl or        C₁-C₆ haloalkyl; and    -   each R²⁴ is independently H, C₁-C₆ alkyl or C₁-C₆ haloalkyl.

Embodiment C

A compound of Embodiment B wherein

-   -   at least one of Q¹ and Q² is phenyl substituted with 2 or 3        substituents independently selected from R³;    -   R¹ is H or CH₃;    -   R² is CH₃;    -   R⁴ is H;    -   each R³ is independently selected from halogen, cyano, C₁-C₃        alkyl, C₁-C₃ haloalkyl, C₁-C₃ alkoxy and C₁-C₃ haloalkoxy; and    -   R¹⁸ is H.

Embodiment D

A compound of Embodiment C wherein

-   -   Q¹ is phenyl substituted at the 2-, 4- and 6-positions with        substituents independently selected from R³; or phenyl        substituted at the 2- and 4-positions with substituents        independently selected from R³; or phenyl substituted at the 2-        and 6-positions with substituents independently selected from        R³;    -   Q² is phenyl substituted at the 2-, 4- and 6-positions with        substituents independently selected from R³; or phenyl        substituted at the 2- and 4-positions with substituents        independently selected from R³; or phenyl substituted at the 2-        and 6-positions with substituents independently selected from        R³;    -   X is O, NR⁴ or CR¹⁵R¹⁶;    -   R¹ is H;    -   each R³ is independently selected from F, Cl, Br, cyano, C₁-C₂        alkyl, C₁-C₂ haloalkyl, C₁-C₂ alkoxy and C₁-C₂ haloalkoxy; and    -   R⁴ is H.

Embodiment E

A compound of Embodiment D wherein

-   -   each R³ is independently selected from F, Cl, Br, cyano, methyl,        C₁-C₂ alkoxy and fluoromethoxy.

Embodiment F

A compound of Embodiment E wherein

-   -   X is O or NH; and    -   each R³ is independently selected from F, Cl, Br, cyano and        methoxy.

Specific embodiments include compounds of Formula 1 selected from thegroup consisting of:

-   4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-N-(2,4,6-trifluorophenyl)-1H-pyrazol-5-amine    (Compound 18),-   N-(4-chlorophenyl)-4-(2,6-difluoro-4-methoxyphenyl)-1,3-dimethyl-1H-pyrazol-5-amine    (Compound 22),-   4-(2,6-difluoro-4-methoxyphenyl)-N-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine    (Compound 23),-   4-(2,6-difluoro-4-methoxyphenyl)-1,3-dimethyl-N-(2,4,6-trifluorophenyl)-1H-pyrazol-5-amine    (Compound 24),-   N-(2,6-difluoro-4-methoxyphenyl)-4-(3,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine    (Compound 36),-   4-(2,4-difluorophenyl)-1,3-dimethyl-N-(2,4,6-trifluorophenyl)-1H-pyrazol-5-amine    (Compound 41),-   4-[[4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-yl]oxy]-3,5-difluorobenzonitrile    (Compound 45),-   4-[[4-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-yl]oxy]-3-fluorobenzonitrile    (Compound 361),-   4-(2-chloro-4-fluorophenyl)-N-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine    (Compound 172),-   4-[[4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-yl]oxy]-3-fluorobenzonitrile    (Compound 118),-   3-chloro-4-[[4-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-yl]oxy]benzonitrile    (Compound 358),-   4-(2-chloro-4-fluorophenyl)-α-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazole-5-methanol-   (Compound 351),-   N,4-bis(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine    (Compound 175),-   N-(2-chloro-4-fluorophenyl)-4-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine    (Compound 193),-   N-(2-chloro-4,6-difluorophenyl)-4-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine    (Compound 297),-   N-(2-chloro-4,6-difluorophenyl)-4-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine    (Compound 343),-   N-(4-chloro-2,6-difluorophenyl)-4-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine    (Compound 349),-   N-(4-chloro-2,6-difluorophenyl)-4-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine    (Compound 357),-   3-chloro-4-[[4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-yl]oxy]benzonitrile    (Compound 139),-   4-[[4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-yl]amino]-3,5-difluorobenzonitrile    (Compound 91),-   4-[[4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-yl]oxy]-2,5-difluorobenzonitrile    (Compound 148),-   N-(2-chloro-4-fluorophenyl)-4-(2,6-difluoro-4-methoxyphenyl)-1,3-dimethyl-1H-pyrazol-5-amine    (Compound 87),-   α,4-bis(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-methanol    (Compound 352),-   N-(4-chloro-2,6-difluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine    (Compound 286),-   N-(2-chloro-4,6-difluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine    (Compound 287),-   N-(2,6-dichloro-4-fluorophenyl)-4-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine    (Compound 368),-   3-chloro-4-[5-[(2-chloro-4,6-difluorophenyl)amino]-1,3-dimethyl-1H-pyrazol-4-yl]-benzonitrile    (Compound 332),-   3-chloro-4-[5-[(4-chloro-2,6-difluorophenyl)amino]-1,3-dimethyl-1H-pyrazol-4-yl]-benzonitrile    (Compound 336),-   N-(2-bromo-4-fluorophenyl)-4-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine    (Compound 346),-   4-(2-chloro-4-fluorophenyl)-N-(2,4-dichloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine    (Compound 367),-   4-(2-chloro-4-fluorophenyl)-N-(2,6-dichloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine    (Compound 369),-   4-[[4-(2-bromo-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-yl]oxy]-3-fluorobenzonitrile    (Compound 284),-   N-(2-bromo-4-fluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine    (Compound 265),-   4-(2-bromo-4-fluorophenyl)-1,3-dimethyl-N-(2,4,6-trifluorophenyl)-1H-pyrazol-5-amine    (Compound 266),-   N-(4-bromo-2,6-difluorophenyl)-4-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine    (Compound 364),-   4-[[4-(2-bromo-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-yl]oxy]-3,5-difluorobenzonitrile    (Compound 232),-   4-(2-bromo-4-fluorophenyl)-N-(2-chloro-4,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine    (Compound 292),-   4-(2-bromo-4-fluorophenyl)-N-(4-chloro-2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine    (Compound 360),-   N-(4-bromo-2,6-difluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine    (Compound 365),-   3-bromo-4-[[4-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-yl]oxy]benzonitrile    (Compound 372),-   3-chloro-4-[[4-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-yl]oxy]benzonitrile    (Compound 373),-   N-(2,4-dichloro-6-fluorophenyl)-4-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine    (Compound 374),-   N-(2,6-dichloro-4-fluorophenyl)-4-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine    (Compound 375),-   N-(2-bromo-4,6-difluorophenyl)-4-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine    (Compound 376),-   N-(2-bromo-4,6-difluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine    (Compound 377),-   N-(4-bromo-2,6-difluorophenyl)-4-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine    (Compound 378),-   N-(2-bromo-4,6-difluorophenyl)-4-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine    (Compound 379),-   N-(2-bromo-4,6-difluorophenyl)-4-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine    (Compound 380),-   α-(4-chloro-2,6-difluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-methanol    (Compound 381),-   4-[5-[(2-chloro-4,6-difluorophenyl)amino]-1,3-dimethyl-1H-pyrazol-4-yl]-3-fluorobenzonitrile    (Compound 382),-   4-[5-[(4-chloro-2,6-difluorophenyl)amino]-1,3-dimethyl-1H-pyrazol-4-yl]-3-fluorobenzonitrile    (Compound 383),-   α-(2-chloro-4,6-difluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-methanol    (Compound 384),-   α-(2-bromo-4-fluorophenyl)-4-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazole-5-methanol    (Compound 385), and-   α-(2-bromo-4-fluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-methanol    (Compound 386).

This invention provides a fungicidal composition comprising a compoundof Formula 1 (including all geometric and stereoisomers, N-oxides, andsalts thereof), and at least one other fungicide. Of note as embodimentsof such compositions are compositions comprising a compoundcorresponding to any of the compound embodiments described above.

This invention provides a fungicidal composition comprising afungicidally effective amount of a compound of Formula 1 (including allgeometric and stereoisomers, N-oxides, and salts thereof), and at leastone additional component selected from the group consisting ofsurfactants, solid diluents and liquid diluents. Of note as embodimentsof such compositions are compositions comprising a compoundcorresponding to any of the compound embodiments described above.

This invention provides a method for controlling plant diseases causedby fungal plant pathogens comprising applying to the plant or portionthereof, or to the plant seed, a fungicidally effective amount of acompound of Formula 1 (including all geometric and stereoisomers,N-oxides, and salts thereof). Of note as embodiment of such methods aremethods comprising applying a fungicidally effective amount of acompound corresponding to any of the compound embodiments describeabove. Of particular note are embodiments where the compounds areapplied as compositions of this invention.

Of note are compounds of Formula 1 that are compounds of Formula 1P(including all geometric and stereoisomers), N-oxides, and saltsthereof, and also agricultural compositions containing them and theiruse as fungicides:

wherein

-   -   Q¹ and Q² are independently phenyl, thienyl, pyridinyl,        pyridazinyl, pyrazinyl or pyrimidinyl, each optionally        substituted with up to 5 substituents independently selected        from R³;    -   X is O, S(O)_(m) or NR⁴;    -   R¹ is H, halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₄ alkenyl,        C₂-C₄ alkynyl, C₃-C₇ cycloalkyl, CO₂R⁵, C(O)NR⁶R⁷, cyano, C₁-C₆        alkoxy, C₁-C₆ haloalkoxy or C₂-C₅ alkoxyalkyl; or    -   R¹ is phenyl optionally substituted with up to 3 R⁸; or a five-        or six-membered nitrogen-containing aromatic heterocycle        optionally substituted with up to 3 substituents independently        selected from R^(9a) on carbon atom ring members and R^(9b) on        nitrogen atom ring members;    -   R² is CH₃, CH₂CH₃, cyclopropyl or halogen;    -   each R³ is independently selected from halogen, cyano, nitro,        amino, methylamino, dimethylamino, C₁-C₄ alkyl, C₁-C₄ haloalkyl,        C₁-C₃ alkoxy, C₁-C₃ haloalkoxy, C₁-C₃ alkylthio, C₁-C₃        haloalkylthio, C₁-C₃ alkylsulfinyl, C₁-C₃ haloalkylsulfinyl,        C₁-C₃ alkylsulfonyl, C₁-C₃ haloalkylsulfonyl, C₃-C₄ cycloalkyl,        C₃-C₇ cycloalkoxy, C₄-C₆ alkylcycloalkyl, C₄-C₆ cycloalkylalkyl,        C₃-C₇ halocycloalkyl, C₂-C₄ alkenyl and C₂-C₄ alkynyl;    -   R⁴ is H, formyl, C₃-C₇ cycloalkyl, —SO₃-M⁺, —SR¹⁰ or —(C═W)R¹¹;        or C₁-C₆ alkyl or C₁-C₆ haloalkyl, each optionally substituted        with up to 2 R¹²;    -   R⁵ is H, C₁-C₆ alkyl or C₁-C₆ haloalkyl;    -   R⁶ and R⁷ are independently selected from H, C₁-C₆ alkyl, C₁-C₆        haloalkyl, C₃-C₇ cycloalkyl, C₄-C₈ cycloalkylalkyl and C₄-C₈        alkylcycloalkyl; or    -   R⁶ and R⁷ are taken together with the nitrogen atom to which        they are connected to form a four- to seven-membered nonaromatic        heterocyclic ring containing ring members, in addition to the        connecting ring nitrogen atom, selected from carbon atoms and        optionally up to one ring member selected from O, S(O)_(n) and        NR¹³;    -   each R⁸, R^(9a) and R^(9b) is independently selected from        halogen, C₁-C₂ alkyl, C₁-C₂ haloalkyl, C₁-C₂ alkoxy, C₁-C₂        haloalkoxy, cyano, nitro, SCH₃, S(O)CH₃ and S(O)₂CH₃;    -   R¹⁰ is C₁-C₆ alkyl or C₁-C₆ haloalkyl;    -   R¹¹ is C₁-C₆ alkyl, C₁-C₆ alkoxy, C₂-C₇ alkoxyalkyl, C₂-C₇        alkylaminoalkyl, C₂-C₈ dialkylaminoalkyl, C₁-C₆ alkylthio or        C₂-C₇ alkylthioalkyl;    -   each R¹² is independently C₃-C₇ cycloalkyl, C₁-C₄ alkoxy, C₁-C₄        haloalkoxy, C₁-C₄ alkylthio, C₁-C₄ alkylsulfinyl or C₁-C₄        alkylsulfonyl;    -   R¹³ is H, C₁-C₃ alkyl or C₂-C₃ haloalkyl;    -   W is O or S;    -   M⁺ is a cation;    -   m is 0, 1 or 2; and    -   n is 0, 1 or 2.

Accordingly of note is a compound selected from Formula 1P (includingall geometric and stereoisomers), N-oxides, and salts thereof, asdefined above. Also of note are counterpart embodiments that areembodiment counterparts to Embodiments 1 through 139 and Embodiments Athrough F wherein in said counterpart embodiments “Formula 1” isreplaced by “Formula 1P” and the scope of said counterpart embodimentsdoes not exceed the scope defined above for Formula 1P. Examples ofcombinations of Embodiments 1 through 139 as applied to Formula 1P areEmbodiments AP, BP, CP, DP and EP:

Embodiment AP

A compound of Formula 1P wherein

-   -   Q¹ is phenyl, pyridinyl, pyrimidinyl, pyrazinyl or pyridazinyl,        each substituted with from 1 to 4 substituents independently        selected from R³;    -   Q² is phenyl, pyridinyl, pyrimidinyl, pyrazinyl or pyridazinyl,        each substituted with 1, 2 or 3 substituents independently        selected from R³    -   X is O or NR⁴;    -   R¹ is H, halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl, CO₂R⁵,        C(O)NR⁶R⁷, cyano, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy or C₂-C₅        alkoxyalkyl; or    -   R¹ is a five- or six-membered nitrogen-containing aromatic        heterocycle optionally substituted with up to 3 substituents        independently selected from R^(9a) on carbon atom ring members        and R^(9b) on nitrogen atom ring members;    -   R² is CH₃, CH₂CH₃, Cl or Br;    -   each R³ is independently selected from halogen, cyano, nitro,        amino, methylamino, dimethylamino, C₁-C₄ alkyl, C₁-C₄ haloalkyl,        C₁-C₃ alkoxy, C₁-C₃ haloalkoxy C₁-C₃ alkylthio, C₁-C₃        haloalkylthio, C₁-C₃ alkylsulfinyl, C₁-C₃ haloalkylsulfinyl,        C₁-C₃ alkylsulfonyl, C₁-C₃ haloalkylsulfonyl and C₃-C₄        cycloalkyl;    -   R⁴ is H, formyl, C₃-C₇ cycloalkyl or —SR¹⁰; or C₁-C₆ alkyl or        C₁-C₆ haloalkyl, each optionally substituted with up to 2 R¹²;    -   R⁵ is H or C₁-C₆ alkyl;    -   R⁶ is H or C₁-C₆ alkyl;    -   R⁷ is H, C₁-C₆ alkyl, C₁-C₆ haloalkyl or C₄-C₈ alkylcycloalkyl;        or    -   R⁶ and R⁷ are taken together with the nitrogen atom to which        they are connected to form a four- to seven-membered nonaromatic        heterocyclic ring containing ring members, in addition to the        connecting nitrogen atom, selected from carbon atoms and up to        one ring member selected from O and NR¹³;    -   each R⁸ is independently selected from halogen, C₁-C₂ alkyl,        C₁-C₂ haloalkyl, C₁-C₂ alkoxy, C₁-C₂ haloalkoxy, cyano and        nitro;    -   each R^(9a) is independently selected from halogen, C₁-C₂ alkyl,        C₁-C₂ haloalkyl, C₁-C₂ alkoxy, C₁-C₂ haloalkoxy, cyano and        nitro;    -   each R^(9b) is C₁-C₂ alkyl;    -   R¹⁰ is CH₃, CH₂CH₃, CF₃ or CF₂CF₃;    -   each R¹² is independently C₃-C₇ cycloalkyl or C₁-C₄ alkoxy; and    -   R¹³ is H or CH₃.

Embodiment BP

A compound of Embodiment AP wherein

-   -   Q¹ is phenyl or pyridinyl, each substituted with 1, 2 or 3        substituents independently selected from R³;    -   Q² is phenyl or pyridinyl, each substituted with 1, 2 or 3        substituents independently selected from R³;    -   X is NR⁴;    -   R¹ is H, halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl, cyano, C₁-C₆        alkoxy or C₁-C₆ haloalkoxy;    -   R² is CH₃;    -   each R³ is independently selected from halogen, cyano, nitro,        C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₃ alkoxy and C₁-C₃ haloalkoxy;    -   R⁴ is H, formyl, C₃-C₇ cycloalkyl or —SR¹⁰; or C₁-C₆ alkyl        substituted with one R¹²;    -   R¹⁰ is CH₃; and    -   each R¹² is independently cyclopropyl or —OCH₃.

Embodiment CP

A compound of Embodiment AP wherein

-   -   Q¹ is phenyl substituted at the 2-, 4- and 6-positions with        substituents independently selected from R³; or    -   Q¹ is phenyl substituted at the 2- and 4-positions with        substituents independently selected from R³;    -   Q² is phenyl substituted at the 2-, 4- and 6-positions with        substituents independently selected from R³;    -   X is O;    -   R² is CH₃;    -   each R³ is independently selected from F, Cl, Br, cyano, nitro,        CH₃, CF₃, —OCH₃, and —OCHF₂; and    -   R⁴ is H, formyl or cyclopropyl.

Embodiment DP

A compound of Embodiment CP wherein

-   -   Q¹ is phenyl substituted at the 2- and 4-positions with        substituents independently selected from R³;    -   Q² is phenyl substituted at the 2-, 4- and 6-positions with        substituents independently selected from R³;    -   each R³ is independently selected from F, Cl, cyano and —OCH₃;        and    -   R⁴ is H.

Embodiment EP

A compound of Embodiment BP wherein

-   -   Q¹ is phenyl substituted at the 2- and 4-positions with        substituents independently selected from R³;    -   Q² is phenyl substituted at the 2-, 4- and 6-positions with        substituents independently selected from R³;    -   each R³ is independently selected from F, Cl, CN and —OCH₃; and    -   R⁴ is H.

Also of note is a fungicidal composition comprising a fungicidallyeffective amount of a compound of Formula 1P (including all geometricand stereoisomers, N-oxides, and salts thereof) or any one ofcounterpart embodiments that are embodiment counterparts to Embodiments1 through 139 and Embodiments A through F (e.g., Embodiment AP, BP, CP,DP or EP), and at least one additional component selected from the groupconsisting of surfactants, solid diluents and liquid diluents. Also ofnote is a method for controlling plant diseases caused by fungal plantpathogens comprising applying to the plant or portion thereof, or to theplant seed, a fungicidally effective amount of a compound of Formula 1P(including all geometric and stereoisomers, N-oxides, and salts thereof)or any one of said counterpart embodiments. Of particular note areembodiments where the compounds of Formula 1P are applied ascompositions of this invention.

One or more of the following methods and variations as described inSchemes 1-24 can be used to prepare the compounds of Formula 1(including Formula 1P). The definitions of Q¹, Q², R¹, R² and m in thecompounds of Formulae 1-33 below are as defined above in the Summary ofthe Invention unless otherwise noted. Formulae 1a, 1b, 1c, 1d, 1e, 1f,1g and 1h are various subsets of Formula 1; Formulae 4a, 4b and 4c arevarious subsets of Formula 4; Formulae 6a and 6b are various subsets ofFormula 6; Formula 11a is a subset of Formula 11; Formula 13a is asubset or analog of Formula 13; and Formula 17a is a subset of Formula17. Substituents for each subset formula are as defined for its parentformula unless otherwise noted.

As illustrated in Scheme 1, sulfoxides and sulfones of Formula 1b (i.e.Formula 1 wherein X is S(O)_(m) and m is 1 or 2) can be made viaoxidation of the linking sulfur atom on sulfides of Formula 1a (i.e.Formula 1 wherein X is S(O)_(m) and m is 0). In this method a compoundof Formula 1b wherein m is 1 (i.e. sulfoxides) or m is 2 (i.e. sulfones)is prepared by oxidizing a corresponding sulfide of Formula 1a with asuitable oxidizing agent. In a typical procedure, an oxidizing agent inan amount from 1 to 4 equivalents depending on the oxidation state ofthe product desired is added to a solution of the compound of Formula 1ain a solvent. Useful oxidizing agents include Oxone® (potassiumperoxymonosulfate), hydrogen peroxide, sodium periodate, peracetic acidand 3-chloroperbenzoic acid. The solvent is selected with regard to theoxidizing agent employed. Aqueous ethanol or aqueous acetone ispreferably used with potassium peroxymonosulfate, and dichloromethane isgenerally preferable with 3-chloroperbenzoic acid. Useful reactiontemperatures typically range from −78 to 90° C. Particular proceduresuseful for oxidizing sulfides to sulfoxides and sulfones are describedby Brand et al., J. Agric. Food Chem. 1984, 32, 221-226 and referencescited therein.

As shown in Scheme 2, compounds of Formula 1 in which X is NH and R^(1a)is H can be prepared by the reaction of 1H-pyrazole compounds of Formula2 with various alkylating agents (e.g., Formula 3), such as iodoalkanes,alkylsulfonates (e.g., mesylate (OMs) or tosylate (OTs)) or trialkylphosphates, preferably in the presence of an organic or inorganic basesuch as 1,8-diazabicyclo[5.4.0]undec-7-ene, potassium carbonate orpotassium hydroxide, and in a solvent such as N,N-dimethylformamide,tetrahydrofuran, toluene or water.

Compounds of Formula 1 wherein CHR¹R^(1a) forms an optionallysubstituted cyclopropyl ring can likewise be prepared by reaction of apyrazole of Formula 2 with an organometallic reagent, such astricyclopropylbismuth, in the presence of a catalyst, such as copperacetate, under conditions known in the art. See, for example, J. Am.Chem. Soc. 2007, 129(1), 44-45. Of note as starting materials in themethod of Scheme 2 are compounds of Formula 2 specifically disclosed inTables 588 through 671 below.

As is shown in Scheme 3, compounds of Formula 1 can be prepared by thereaction of compounds of Formula 4 (i.e. 5-aminopyrazoles for X beingNR⁴, 5-hydroxypyrazoles (5-pyrazolones) for X being O, or5-mercaptopyrazoles for X being S) with aromatic compounds of Formula 5containing a leaving group G (i.e. halogen or (halo)alkylsulfonate),optionally in the presence of a metal catalyst, and generally in thepresence of a base and a polar aprotic solvent such asN,N-dimethylformamide or dimethyl sulfoxide. For example, compounds ofFormula 5 in which Q² is an electron-deficient heteroaromatic ring, or abenzene ring with electron-withdrawing substituents, react by directdisplacement of the leaving group G from the ring to provide compoundsof Formula 1. For compounds of Formula 5 wherein Q² is attached througha sp³-hybridized carbon atom, G is typically Cl, Br, I or a sulfonate(e.g., OS(O)₂CH₃). Compounds of Formula 5 are commercially available ortheir preparation is known in the art. Of note are embodiments of themethod of Scheme 3 wherein a compound of Formula 4 is used to prepare acorresponding compound of Formula 1 specifically disclosed in Tables 85through 252 below.

For reactions according to the method of Scheme 3 of a compound ofFormula 4 wherein X is O or NR⁴ with a compound of Formula 5 (Q²-G)wherein Q is an aromatic or heteroaromatic ring Q lacking sufficientlyelectron-withdrawing substituents, or to improve reaction rate, yield orproduct purity, the use of a metal catalyst (e.g., metal or metal salt)in amounts ranging from catalytic up to superstoichiometric canfacilitate the desired reaction. Typically for these conditions, G is Bror I or a sulfonate such as OS(O)₂CF₃ or OS(O)₂(CF₂)₃CF₃. For example,copper salt complexes (e.g., CuI with N,N′-dimethyl-ethylenediamine,proline or bipyridyl), palladium complexes (e.g.,tris(dibenzylidene-acetone)dipalladium(0)) or palladium salts (e.g.,palladium acetate) with ligands such as4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (i.e. “Xantphos”),2-dicyclohexyl-phosphino-2′,4′,6′-triisopropylbiphenyl (i.e. “Xphos”) or2,2′-bis(diphenylphosphino)-1,1′-binaphthalene (i.e. “BINAP”), in thepresence of a base such as potassium carbonate, cesium carbonate, sodiumphenoxide or sodium tert-butoxide, in a solvent such asN,N-dimethylformamide, 1,2-dimethoxyethane, dimethyl sulfoxide,1,4-dioxane or toluene, optionally mixed with alcohols such as ethanol,can be used. Alternatively as illustrated in Scheme 4, compounds ofFormula 1c (i.e. Formula 1 in which X is NR⁴ and R⁴ is H) can beprepared by reaction of compounds of Formula 6 (i.e. 5-bromopyrazoles orother pyrazoles substituted at the 5-position with a leaving group) withcompounds of Formula 7 under metal-catalyzed conditions similar to thosedescribed above for Scheme 3. Compounds of Formula 7 are commerciallyavailable or their preparation is known in the art.

As shown in Scheme 5, compounds of Formula 6 wherein G is Br or I can beprepared by reaction of 5-aminopyrazoles of Formula 4a (i.e. Formula 4wherein X is NH) under diazotization conditions either in the presenceof, or followed by combination with, copper salts containing bromide oriodide. For example, addition of tert-butyl nitrite to a solution of a5-aminopyrazole of Formula 4a in the presence of CuBr₂ in a solvent suchas acetonitrile provides the corresponding 5-bromopyrazole of Formula 6.Likewise, a 5-aminopyrazole of Formula 4a can be converted to adiazonium salt and then to a corresponding 5-halopyrazole of Formula 6by treatment with sodium nitrite in solvents such as water, acetic acidor trifluoroacetic acid, in the presence of a mineral acid typicallycontaining the same halide atom (such as aqueous HI solution for G beingI), followed by treatment with the corresponding copper(I) or copper(II)salt according to general procedures well known to those skilled in theart.

As shown in Scheme 6, 5-bromopyrazoles of Formula 6a (i.e. Formula 6wherein G is Br) can be prepared by reacting 5-hydroxypyrazoles ofFormula 4b (i.e. Formula 4 wherein X is O) with phosphorus tribromide asdescribed in Tetrahedron Lett. 2000, 41(24), 4713.

As shown in Scheme 7, 5-hydroxypyrazoles of Formula 4b can also be usedto prepare 5-fluoroalkylsulfonyl (e.g, 5-trifluoromethanesulfonyl,5-nonafluorobutylsulfonyl) pyrazoles of Formula 6b (i.e. Formula 6wherein G is fluoroalkylsulfonyl) as described in Synlett 2004, 5, 795.

-   -   wherein Rf is fluoroalkyl such as CF₃ or (CF₂)₂CF₃

As shown in Scheme 8, compounds of Formula 1 can be prepared by reactionof 4-bromo or iodo pyrazoles of Formula 10 wherein X is O, NR⁴, C(═O) orS(O)_(m) in which m is 2 with organometallic compounds of formula Q¹-M(Formula 11) under transition-metal-catalyzed cross-coupling reactionconditions. Reaction of a 4-bromo or iodo pyrazole of Formula 10 with aboronic acid, trialkyltin, zinc or organomagnesium reagent of Formula 11in the presence of a palladium or nickel catalyst having appropriateligands (e.g., triphenylphosphine (PPh₃), dibenzylideneacetone (dba),dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-2-yl)phosphine (SPhos)) anda base, if needed, affords the corresponding compound of Formula 1. Forexample, a substituted aryl boronic acid or derivative (e.g., Formula 11wherein Q¹ is optionally substituted phenyl or heterocyclyl and M isB(OH)₂, B(OC(CH₃)₂C(CH₃)₂O)) or B(O-i-Pr)₃/Li— reacts with a 4-bromo- or4-iodopyrazole of Formula 10 in the presence ofdichlorobis(triphenylphosphine) palladium(II) and aqueous base such assodium carbonate or potassium hydroxide, in solvents such as1,4-dioxane, 1,2-dimethoxyethane, toluene or ethyl alcohol, or underanhydrous conditions with a ligand such as phosphine oxide or phosphiteligand (e.g., diphenylphosphine oxide) and potassium fluoride in asolvent such as 1,4-dioxane (see Angewandte Chemie, InternationalEdition 2008, 47(25), 4695-4698) to provide the corresponding compoundof Formula 1.

As illustrated in Scheme 9, compounds of Formula 4a (i.e. Formula 4wherein X is NH) can be prepared by reacting compounds of Formula 12with compounds of Formula 11 (such as Q¹-B(OH)₂ (Formula 11a)) usingtransition-metal-catalyzed cross-coupling reaction conditions asdescribed for the method of Scheme 8.

As illustrated in Scheme 10, pyrazoles of Formula 10 wherein X is O,S(O)₂, NR⁴ or C(═O) and G is Br or I are readily prepared by thereaction of pyrazoles unsubstituted at the 4-position (Formula 13) withhalogenating reagents such as bromine, sodium bromite,N-bromosuccinimide (NBS) or N-iodosuccinimide (NIS), in solvents such asacetic acid, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamideor 1,4-dioxane, or a mixture of water with the aforementioned solvents,at temperatures ranging from ambient to the boiling point of thesolvent.

Furthermore, using reaction conditions similar to those for the methodof Scheme 10, compounds of Formula 13 wherein A is H or a protectinggroup can be converted into intermediates corresponding to Formula 10wherein Q² is replaced by A or a protecting group, respectively, whichare useful for preparing compounds of Formula 1. Compounds of Formula 13wherein A is H can be prepared by methods known in the art; see, forexample, Synlett 2004, 5, 795-798, U.S. Pat. No. 4,256,902 andreferences cited therein. Furthermore, some compounds of Formula 13wherein A is H, particularly those in which R² is methyl, ethyl orhalogen, are commercially available.

As shown in Scheme 11, compounds of Formula 13 wherein X is O, S(O)_(m)or NR⁴, m is 0, and A is Q² can be prepared from corresponding compoundsof Formula 13a (i.e. Formula 13 wherein A is H) by procedures analogousthose used for the method of Scheme 3. Compounds of Formula 13 wherein Xis S (i.e. S(O)_(m) wherein m is 0) can then be oxidized usingprocedures such as those used for the method of Scheme 1 to providecorresponding compounds of Formula 13 wherein X is S(O)₂ for use in themethod of Scheme 10. Compounds of Formula 13a are commercially availableor can be prepared by methods known in the art.

As shown in Scheme 12, compounds of Formula 1a (i.e. Formula 1 wherein Xis S(O)_(m) and m is 0), Formula 1d (i.e. Formula 1 wherein X isCR¹⁵R¹⁶, R¹⁵ is H, R¹⁶ is OR¹⁸ and R¹⁸ is H) and Formula 1e (i.e.Formula 1 wherein X is C(═O)) can be prepared by treatment of compoundsof Formula 6 with an organometallic reagent (i.e. Formula 26) such as analkyllithium, preferably n-butyllithium, or an alkylmagnesium reagent,preferably isopropylmagnesium chloride (optionally complexed withlithium chloride), followed by the addition of a sulfur electrophile(i.e. Formula 27) or carbonyl electrophile (i.e. Formula 28, 29 or 30).Reaction temperatures can range from −90° C. to the boiling point of thereaction solvent; temperatures of −78° C. to ambient temperature aregenerally preferred, with temperatures of −78 to −10° C. preferred whenan alkyllithium reagent is used, and −20° C. to ambient temperaturepreferred with use of alkylmagnesium reagents. A variety of solvents areuseful, such as toluene, ethyl ether, tetrahydrofuran ordimethoxymethane; anhydrous tetrahydrofuran is preferred. A secondmetallic component, such as zinc chloride, zinc bromide or a monovalentcopper salt, such as copper(I) iodide or copper(I) cyanide, canadvantageously be added before the electrophile in cases in which theelectrophile is Q²C(O)Cl (i.e. Formula 30). The Q²-containing sulfur andcarbonyl intermediates of Formulae 27, 28, 29 and 30 are commerciallyavailable or can be prepared by methods known in the art.

It will be recognized by one skilled in the art that reactions analogousto those shown in Scheme 12 can also be utilized with pyrazoles lackinga Q¹ substituent, thus affording certain compounds of Formula 13 thatare useful in the method outlined in Scheme 10.

General methods useful for preparing 5-aminopyrazoles of Formula 4a arewell known in the art; see, for example, Journal fir Praktische Chemie(Leipzig) 1911, 83, 171 and J. Am. Chem. Soc. 1954, 76, 501. Such amethod is illustrated in Scheme 13 in which R² is alkyl or cycloalkyl.

Similarly, general methods useful for preparing 5-hydroxypyrazoles ofFormula 4b are well known in the art; see, for example, Annalen derChemie 1924, 436, 88. Such a method is illustrated in Scheme 14 in whichR² is alkyl or cycloalkyl.

As shown in Scheme 15, 5-thiopyrazole compounds of Formula 4c (i.e.Formula 4 wherein X is S) can be prepared by reaction of corresponding5-hydroxypyrazole compounds of Formula 4b with P₂S₅ (see, for example,Justus Liebigs Annalen der Chemie 1908, 361, 251) or with Lawesson'sReagent (2,4-bis-(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane2,4-disulfide; see, for example, International Patent Publication WO2005/118575) in solvents such as toluene, xylene or tetrahydrofuran.

As shown in Scheme 16, compounds of Formula 1c (i.e. Formula 1 wherein Xis NR⁴ and R⁴ is H) can be prepared by condensing compounds of Formula17 with alkylhydrazines of Formula 15 in a solvent such as ethanol ormethanol and optionally in the presence of an acid or base catalyst suchas acetic acid, piperidine or sodium methoxide, according to generalprocedures known in the art.

-   -   wherein R³² is H or lower alkyl (e.g., CH₃, CH₂CH₃ or (CH₂)₂CH₃)

In a manner analogous to the method of Scheme 16, compounds of Formula 2wherein X is NH can be similarly prepared by condensing compounds ofFormula 17 with hydrazine. This method is described in Chemistry ofHeterocyclic Compounds 2005, 41(1), 105-110.

As shown in Scheme 17, compounds of Formula 17 (wherein, e.g., R² ismethyl, ethyl or optionally substituted cyclopropyl and R³³ is H orlower alkyl such as CH₃, CH₂CH₃ or (CH₂)₂CH₃) can be prepared byreaction of corresponding ketene dithioacetal compounds of Formula 18with compounds of formula Q²-NH₂ (i.e. Formula 7) optionally in thepresence of a base, such as sodium hydride or ethylmagnesium chloride,in solvents such as toluene, tetrahydrofuran or dimethoxymethane, attemperatures ranging from −10° C. to the boiling point of the solvent.See, for example, J. Heterocycl. Chem. 1975, 12(1), 139. Methods usefulfor preparing compounds of Formula 18 are known in the art.

-   -   wherein R³³ is H or lower alkyl (e.g., CH₃, CH₂CH₃ or (CH₂)₂CH₃)

It is also known in the art (see, for example, Synthesis 1989, 398) thatcompounds of Formula 18 in which the two R³³ groups are taken togetheras a single CH₂ group (thus forming a dithietane ring) react with anstoichiometric excess amount of hydrazines of Formula 15 to affordcompounds of Formula 4c, which are useful for preparation of compoundsof Formula 1 in which X is S according to the method of Scheme 3.

As shown in Scheme 18, compounds of Formula 17a (i.e. tautomer ofFormula 17 wherein R³³ is H) can be prepared by reaction ofcorresponding isothiocyanate compounds of Formula 19 with arylacetonecompounds of Formula 20 wherein R² is methyl, ethyl or optionallysubstituted cyclopropyl; see, for example, Zhurnal Organicheskoi Khimii1982, 18(12), 2501. Bases useful for this reaction include sodiumhydride, alkoxide bases (e.g., potassium tert-butoxide or sodiumethoxide), potassium hydroxide, sodium hydroxide, potassium carbonate,or amine bases (e.g., triethylamine or N,N-diisopropylethylamine). Avariety of solvents are useful, such as tetrahydrofuran, ether, toluene,N,N-dimethylformamide, alcohols (e.g., ethanol), esters (e.g., ethylacetate or isopropyl acetate), or mixtures thereof. Solvents are chosenfor compatibility with the base selected, as is well-known in the art.Reaction temperatures can range from −78° C. to the boiling point of thesolvent. One useful mixture of base and solvent is potassiumtert-butoxide in tetrahydrofuran, to which at −70 to 0° C. is added acombined solution of an isothiocyanate of Formula 19 and a carbonylcompound of Formula 20.

Ketothioamides of Formula 17 can be also be prepared by allowing thecorresponding ketoamides to react with sulfurizing agents such asLawesson's reagent or P₂S₅; see, for example, Helv. Chim. Act. 1998,81(7), 1207.

Compounds of Formula 2 wherein X is NH and R² is Cl or Br, which areuseful for preparing compounds of Formula 1 according to the method ofScheme 2, can be prepared by reaction of corresponding compounds ofFormula 31 with POCl₃ or POBr₃ using general procedures known in theart, as shown in Scheme 19.

As shown in Scheme 20, compounds of Formula 1f (i.e. Formula 1 whereinR¹ and R^(1a) are H and R² is OCH₃) can be prepared by reactingcorresponding compounds of Formula 31 with diazomethane or iodomethanein the presence of base using general procedures known in the art, suchas those described in J. Heterocyclic Chem. 1988, 1307-1310.

Compounds of Formula 1g (i.e. Formula 1 wherein R¹ and R^(1a) are H andR² is SCH₃) can be prepared by treating corresponding compounds ofFormula 31 with P₂S₅ or Lawesson's Reagent to prepare compounds ofFormula 32, which are then reacted with diazomethane or iodomethane inthe presence of base using general procedures known in the art, as shownin Scheme 21.

As shown in Scheme 22, compounds of Formula 31 wherein X is NH can beprepared by condensation of corresponding isothiocyanates of Formula 19with esters of Formula 33 wherein R³³ is lower alkyl (e.g., methyl,ethyl, propyl) in the presence of a strong, non-nucleophilic base suchas sodium hydride or lithium hexamethyldisilazide, in an inert solventsuch as tetrahydrofuran (analogous to the method of Scheme 18), followedby reaction of the intermediate with hydrazine or an acid salt ofhydrazine, such as, for example, an acetate or hydrochloride salt(analogous to the method of Scheme 16).

One skilled in the art will recognize that use of a substitutedhydrazine of formula H₂NNHCHR¹R^(1a) instead of unsubstituted hydrazinein the method of Scheme 22, followed by the further manipulationsdescribed for Schemes 19, 20 and 21 will also afford compounds ofFormula 1.

Compounds of Formula 1c (i.e. Formula 1 wherein X is NR⁴ and R⁴ is H) inwhich R² is halogen can also be prepared as shown in Scheme 23. In thismethod an acetonitrile compound of Formula 21 is condensed with anisothiocyanate compound of Formula 22 in the presence of a base such assodium hydride or potassium tert-butoxide, in a solvent such asN,N-dimethylformamide or tetrahydrofuran, to afford a cyano ketoamideintermediate compound, which is then reacted with a methylating agentsuch as iodomethane or dimethyl sulfate, in the presence of a base toprovide the corresponding compound of Formula 23. Alternatively, themethylating agent can be included in the reaction mixture with thecompounds of Formulae 21 and 22 without isolation of the cyano ketoamideintermediate. One skilled in the art will recognize that compounds ofFormula 23 can also be prepared by a method analogous to Scheme 17wherein the C(O)R² of the compound of Formula 18 is replaced by cyano.According to the method of Scheme 23, the resultant compound of Formula23 is then reacted with an alkylhydrazine of Formula 15 to form thecorresponding 3-aminopyrazole compound of Formula 24 using generalprocedures known in the art; see, for example, J. Chem. Soc. Perkin 11988, 2, 169-173 and J. Med. Chem. 2003, 46(7), 1229-1241. The aminogroup of the compound of Formula 24 can then be converted to R² beinghalogen in Formula 1c by a diazotization reaction using conditions knownin the art, such as those previously described for Scheme 5.

Analogous to the method of Scheme 23, compounds of Formula 2 wherein Xis NH and R² is halogen can be similarly prepared by condensingcompounds of Formula 23 with hydrazine instead of an alkylhydrazine ofFormula 15.

As shown in Scheme 24, compounds of Formula 1h (i.e. Formula 1 wherein Xin NR⁴) can be prepared by reacting corresponding compounds of Formula1c (i.e. Formula 1 wherein X is NH) with an electrophile comprising R⁴(i.e. Formula 25) typically in the presence of a base such as NaH and apolar solvent such as N,N-dimethylformamide. In this context theexpression “electrophile comprising R⁴” means a chemical compoundcapable of transferring an R⁴ moiety to a nucleophile (such as thenitrogen atom attached to Q² in Formula 1c). Often electrophilescomprising R⁴ have the formula R⁴Lg wherein Lg is a nucleofuge (i.e.leaving group in nucleophilic reactions). Typical nucleofuges includehalogens (e.g., Cl, Br, I) and sulfonates (e.g., OS(O)₂CH₃, OS(O)₂CF₃,OS(O)₂-(4-CH₃-Ph)). However, some electrophiles comprising R⁴ do notcomprise a nucleofuge; an example is sulfur trioxide (SO₃), which afterdeprotonation (such as by a base of the formulae M⁺H⁻ wherein M⁺ is acation) of the nitrogen atom attached to Q² in Formula 1c, can bond tothe nitrogen atom as a —SO₃ ⁻M⁺ substituent.

It is recognized by one skilled in the art that various functionalgroups can be converted into others to provide different compounds ofFormula 1. For example, compounds of Formula 1 in which R² is methyl,ethyl or cyclopropyl can be modified by free-radical halogenation toform compounds of Formula 1 wherein R² is halomethyl, haloethyl orhalocyclopropyl. The halomethyl compounds can be used as intermediatesto prepare compounds of Formula 1 wherein R² is hydroxymethyl orcyanomethyl. Compounds of Formula 1 or intermediates for theirpreparation may contain aromatic nitro groups, which can be reduced toamino groups, and then be converted via reactions well known in the artsuch as the Sandmeyer reaction, to various halides, providing othercompounds of Formula 1. By similar known reactions, aromatic amines(anilines) can be converted via diazonium salts to phenols, which canthen be alkylated to prepare compounds of Formula 1 with alkoxysubstituents. Likewise, aromatic halides such as bromides or iodidesprepared via the Sandmeyer reaction can react with alcohols undercopper-catalyzed conditions, such as the Ullmann reaction or knownmodifications thereof, to provide compounds of Formula 1 that containalkoxy substituents. Additionally, some halogen groups, such as fluorineor chlorine, can be displaced with alcohols under basic conditions toprovide compounds of Formula 1 containing the corresponding alkoxysubstituents. The resultant alkoxy compounds can themselves be used infurther reactions to prepare compounds of Formula 1 wherein R³ is —U—V-T(see, for example, PCT Publication WO 2007/149448 A2). Compounds ofFormula 1 or precursors thereof in which R² or R³ is halide, preferablybromide or iodide, are particularly useful intermediates for transitionmetal-catalyzed cross-coupling reactions to prepare compounds ofFormula 1. These types of reactions are well documented in theliterature; see, for example, Tsuji in Transition Metal Reagents andCatalysts: Innovations in Organic Synthesis, John Wiley and Sons,Chichester, 2002; Tsuji in Palladium in Organic Synthesis, Springer,2005; and Miyaura and Buchwald in Cross Coupling Reactions: A PracticalGuide, 2002; and references cited therein.

One skilled in the art will recognize that sulfide groups can beoxidized to the corresponding sulfoxides or sulfones by conditionswell-known in the art. Likewise, compounds of Formula 1 wherein X isCR¹⁵R¹⁶, R¹⁵ is H, R¹⁶ is OR¹⁸ and R¹⁸ is H can be readilyinterconverted with corresponding compounds of Formula 1 wherein X isC(═O) by alcohol oxidation and ketone reduction reactions well known inthe art. Compounds of Formula 1 wherein X is C(═O) (i.e. ketones) can bereadily converted to ketals using general methods known in the art, thusproviding compounds of Formula 1 wherein X is CR¹⁵R¹⁶ and R¹⁵ and R¹⁶are taken together as —OCH₂CH₂O—. Compounds of Formula 1 wherein X isC(═O) can also be converted by the use of Lawesson's Reagent to preparecorresponding compounds of Formula 1 wherein X is C(═S). Furthermore,compounds of Formula 1 wherein X is CR¹⁵R¹⁶, R¹⁵ is C₁-C₄ alkyl, R¹⁶ isOR¹⁸, and R¹⁸ is H can be prepared by adding an alkyl Grignard reagentto the corresponding compounds of Formula 1 wherein X is C(═O).

The above reactions can also in many cases be performed in alternatesequence, such as the preparation of 1H pyrazoles for use in thereaction in Scheme 2 by reactions illustrated later for the generalpreparation of substituted pyrazoles. The presence of certain functionalgroups may not be compatible with all of these reaction conditions, andthe use of protecting groups may be desirable for obtaining the desiredproducts with improved yields and or purity.

It is recognized that some reagents and reaction conditions describedabove for preparing compounds of Formula 1 may not be compatible withcertain functionalities present in the intermediates. In theseinstances, the incorporation of protection/deprotection sequences orfunctional group interconversions into the synthesis will aid inobtaining the desired products. The use and choice of the protectinggroups will be apparent to one skilled in chemical synthesis (see, forexample, Greene, T. W.; Wuts, P. G. M. Protective Groups in OrganicSynthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art willrecognize that, in some cases, after the introduction of a given reagentas it is depicted in any individual scheme, it may be necessary toperform additional routine synthetic steps not described in detail tocomplete the synthesis of compounds of Formula 1. One skilled in the artwill also recognize that it may be necessary to perform a combination ofthe steps illustrated in the above schemes in an order other than thatimplied by the particular sequence presented to prepare the compounds ofFormula 1. One skilled in the art will also recognize that compounds ofFormula 1 and the intermediates described herein can be subjected tovarious electrophilic, nucleophilic, radical, organometallic, oxidation,and reduction reactions to add substituents or modify existingsubstituents.

Without further elaboration, it is believed that one skilled in the artusing the preceding description can utilize the present invention to itsfullest extent. The following Synthesis Examples are, therefore, to beconstrued as merely illustrative, and not limiting of the disclosure inany way whatsoever. Steps in the following Synthesis Examples illustratea procedure for each step in an overall synthetic transformation, andthe starting material for each step may not have necessarily beenprepared by a particular preparative run whose procedure is described inother Examples or Steps. Percentages are by weight except forchromatographic solvent mixtures or where otherwise indicated. Parts andpercentages for chromatographic solvent mixtures are by volume unlessotherwise indicated. ¹H NMR spectra are reported in ppm downfield fromtetramethylsilane in CDCl₃ unless otherwise noted; “s” means singlet,“m” means multiplet, “br s” means broad singlet. Mass spectra arereported as the molecular weight of the highest isotopic abundanceparent ion (M+1) formed by addition of H⁺ (molecular weight of 1) to themolecule, observed by mass spectrometry using atmospheric pressurechemical ionization (AP⁺) where “amu” stands for atomic mass units.

Synthesis Example 1 Preparation ofN-(3-Chlorophenyl)-4-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine(Compound 1) Step A: Preparation ofα-Acetyl-2,4-difluorobenzeneacetonitrile (Alternatively Named methylα-cyano-2,4-difluorobenzeneacetate)

Sodium hydride (60% in mineral oil) (1.5 g, 38 mmol) was stirred inxylenes (7 mL) under a nitrogen atmosphere at ambient temperature. Asolution of anhydrous ethanol (6.3 mL, 64 mmol) in xylenes (2 mL) wasadded dropwise over about 20 minutes at a temperature of about 40° C.The reaction mixture was heated to 70° C., and a solution of2,4-difluorophenylacetonitrile (3.9 g, 25 mmol), ethyl acetate (3.8 mL,38 mmol) and xylenes (1 mL) was added dropwise over 15 min. Additionalxylenes (5 mL) was added to aid stirring. The reaction mixture washeated for 2 h, then allowed to cool. Water (50 mL) was added, and themixture was extracted with hexanes (50 mL). The aqueous phase was thenacidified to pH 3-4 with 1 N aqueous HCl solution. The aqueous phase wasextracted with ether (50 mL), and the ethereal extract was washed withwater (25 mL) and brine, then dried over MgSO₄, and concentrated to givethe title compound as a viscous residue (3.3 g). ¹H NMR δ 7.42 (m, 1H),6.8-7.0 (m, 2H), 4.95 (s, 1H), 2.36 (s, 3H).

Step B: Preparation of4-(2,4-Difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine

Acetic acid (0.5 mL, 8.3 mmol) and methylhydrazine (534 μL, 10.0 mmol)were added to a solution of the residue obtained in Step A (1.6 g, 8.5mmol) in ethyl alcohol (8 mL). The reaction mixture was then heated atreflux for 16 h under a nitrogen atmosphere. While the reaction mixturewas still warm, water was added in small portions (1 mL at a time) untila precipitate formed (about 12 mL of water total). The mixture wasreheated to dissolve the solids and then allowed cooled to roomtemperature. The resulting precipitate was collected on a glass frit,washed with 2 to 3 mL of 50% aqueous ethyl alcohol, and dried undervacuum to obtain the compound as a white solid (0.99 g).

¹H NMR δ 7.20 (m, 1H), 6.92 (m, 2H), 3.68 (s, 3H), 3.47 (br s, 2H), 2.14(s, 3H).

Step C: Preparation ofN-(3-Chlorophenyl)-4-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine

Palladium(II) acetate (90 mg, 0.40 mmol),4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (460 mg, 0.80 mmol) andpowdered potassium carbonate (5.5 g, 40 mmol) were combined in anhydrous1,4-dioxane (20 mL), and the mixture was sparged with a subsurfacestream of N₂ gas for 10 min.4-(2,4-Difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine (i.e. the productof Step B) (0.89 g, 4.0 mmol) was added in one portion, and1-bromo-3-chlorobenzene (0.47 mL, 4.0 mmol) was added via a syringe. Thereaction mixture was heated at reflux under a nitrogen atmosphere for 3h. Additional 1-bromo-3-chlorobenzene (0.09 mL, 0.8 mmol) was added, andheating was continued for 1 h. The reaction mixture was allowed to coolto room temperature, and then partitioned between water (40 mL) andethyl acetate (40 mL). The organic phase was washed with additionalwater (40 mL), brine (40 mL), dried over MgSO₄ and concentrated underreduced pressure. The residue was purified by column chromatographythrough 10 g of silica gel eluted with hexanes/ethyl acetate (1:1) togive the title compound, a compound of the present invention, as a solid(0.41 g).

¹H NMR δ 7.2-7.3 (m, 2H), 7.10 (m, 1H), 6.9-7.0 (m, 2H), 6.70 (m, 1H),6.58 (m, 1H), 6.52 (m, 1H), 3.64 (s, 3H), 2.14 (s, 3H). MS: 334 amu.

Synthesis Example 2 Preparation of4-(2-Chloro-4-fluorophenyl)-N-(2,6-difluoro-4-methoxyphenyl)-1,3-dimethyl-1H-pyrazol-5-amine(Compound 17) Step A: Preparation of5-Bromo-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole

Copper(II) bromide (3.94 g, 17.7 mmol) was added to a solution of4-[2-chloro-4-fluorophenyl]-1,3-dimethyl-1H-pyrazol-5-amine (preparedsimilarly to the preparation of4-(2,4-Difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine in Steps A and Bof Synthesis Example 1) (2.4 g, 10 mmol) in acetonitrile (50 mL), andthe mixture was stirred and cooled in an ice-water bath while tert-butylnitrite (90% technical grade, 2.33 mL, 17.7 mmol) was added dropwiseover 5 min. The reaction mixture was allowed to warm slowly to ambienttemperature. Aqueous HCl solution (20 mL) was added, and then ethylacetate was added (20 mL). This mixture was filtered through a 2-cm padof Celite® diatomaceous filter aid. The filter pad was washed with ethylacetate (20 mL), and the phases were separated. The organic phase waswashed with 1.0 N aqueous hydrochloric acid solution and brine, driedover MgSO₄, and concentrated to leave the title compound as anorange-brown semisolid (2.8 g).

¹H NMR δ 7.18-7.25 (m, 2H), 7.04 (m, 1H), 3.89 (s, 3H), 2.14 (s, 3H).

Step B: Preparation of4-(2-Chloro-4-fluorophenyl)-N-(2,6-difluoro-4-methoxyphenyl)-1,3-dimethyl-1H-pyrazol-5-amine

5-Bromo-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole (i.e. theproduct of Step A) (0.20 g, 0.66 mmol), palladium(II) acetate (15 mg,0.066 mmol), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (76 mg,0.13 mmol) and powdered potassium carbonate (1.8 g, 13 mmol) werecombined in anhydrous 1,4-dioxane (3 mL), and the mixture was spargedwith a subsurface stream of N₂ gas for 10 min.2,6-Difluoro-4-methoxyaniline (0.22 g, 1.3 mmol) was added in oneportion, and the reaction mixture was heated at reflux for 22 h. Thereaction mixture was filtered through Celite® diatomaceous filter aid,and the filter pad was washed with ethyl acetate (20 mL). The filtratewas washed with water (10 mL) and brine (10 mL), dried over MgSO₄, andconcentrated to leave a semisolid residue. This residue was purified bycolumn chromatography through 5 g of silica gel eluted with a gradientof hexanes/ethyl acetate (20:1 to 1:3) to give the title compound, acompound of the present invention, as a light-brown solid (48 mg).

¹H NMR δ 7.0-7.1 (m, 2H), 6.85 (m, 1H), 6.26 (m, 2H), 4.84 (br s, 1H),3.78 (s, 3H), 3.66 (s, 3H), 2.08 (s 3H). MS: 382 amu.

Synthesis Example 3 Preparation of4-(2,6-Difluoro-4-methoxyphenyl)-1,3-dimethyl-N-(2,4,6-trifluorophenyl)-1H-pyrazol-5-amine(Compound 24) Step A: Preparation of2,6-Difluoro-4-methoxybenzeneacetonitrile

A solution of KCN (0.88 g, 13 mmol) dissolved in water (2 mL) was addeddropwise to a water-bath-cooled solution of 2,6-difluoro-4-methoxybenzylbromide (2.50 g, 10.5 mmol) in N,N-dimethylformamide (10 mL). Thereaction mixture was stirred for 20 min. Water was added (20 mL) andthen the reaction mixture was poured into saturated aqueous NaHCO₃solution (20 mL) and extracted with ether (50 mL). The organic phase waswashed with water (5×25 mL), dried over MgSO₄, and concentrated to givean oil, which crystallized on standing to provide the title compound asa white solid (1.9 g).

¹H NMR δ 6.50 (m, 2H), 3.80 (s, 3H), 3.65 (s, 2H).

Step B: Preparation ofca-Acetyl-2,6-difluoro-4-methoxybenzeneacetonitrile

Solid sodium ethoxide (4.7 g, 66 mmol) was stirred in a mixture ofxylene (20 mL) and ethanol (10 mL) and heated to 50° C. A solution of2,6-difluoro-4-methoxybenzeneacetonitrile (i.e. the product of Step A)(8.0 g, 44 mmol) in ethyl acetate (10.4 mL) was added dropwise. Thereaction mixture was heated at 50° C. for 4 h and then allowed to coolto ambient temperature. The reaction mixture was poured into water (100mL) and extracted with ethyl acetate (25 mL). The aqueous phase wasacidified with 3 N aqueous HCl to pH 4 and extracted with ethyl acetate(100 mL). This organic phase was washed with water (50 mL), brine (50mL), then dried over MgSO₄, and concentrated to leave the title compoundas a tan semisolid (8.0 g).

¹H NMR δ 6.56 (m, 2H), 4.86 (s, 1H), 3.83 (s, 3H), 2.40 (s, 3H).

Step C: Preparation of4-(2,6-Difluoro-4-methoxyphenyl)-1,3-dimethyl-1H-pyrazole-5-amine

α-Acetyl-2,6-difluoro-4-methoxybenzeneacetonitrile (i.e. the product ofStep B) (8.03 g, 35.7 mmol) and acetic acid (5 mL) were stirred inethanol (35 mL), and methylhydrazine (1.91 mL, 35.7 mmol) was added. Thereaction mixture was heated at reflux for 16 h, cooled, and then pouredinto water (100 mL). The resulting mixture was extracted with ethylacetate (100 mL). The organic phase was washed with 1 N aqueous NaOH (50mL) and then brine (50 mL), dried over MgSO₄, and concentrated to leavea solid. The solid was dissolved in methanol, and the resulting solutionwas warmed to 45° C.

Water (25 mL) was added dropwise, and the mixture was allowed to cool.The precipitate was collected on a glass frit to give the title compoundas a white solid (3.88 g).

¹H NMR δ 6.55 (m, 2H), 3.81 (s, 3H), 3.67 (s, 3H), 3.43 (br s, 2H), 2.09(s, 3H).

Step D: Preparation of5-Bromo-4-(2,6-difluoro-4-methoxyphenyl)-1,3-dimethyl-1H-pyrazole

Copper(II) bromide (3.81 g, 16.9 mmol) was added to a solution of4-(2,6-difluoro-4-methoxyphenyl)-1,3-dimethyl-1H-pyrazole (i.e. theproduct of Step C) (3.88 g, 15.4 mmol) in acetonitrile (50 mL), and themixture was stirred and cooled in an ice-water bath while tert-butylnitrite (90% technical grade, 3.54 mL, 26.9 mmol) was added dropwiseover 5 min. The reaction mixture was allowed to warm slowly to ambienttemperature. Aqueous hydrochloric acid solution (25 mL) was added, thenethyl acetate (25 mL) was added, and the resulting mixture was filteredthrough a 2-cm pad of Celite® diatomaceous filter aid. The filter padwas washed with ethyl acetate (50 mL), and the phases were separated.The organic phase was washed with 1 N aqueous HCl solution (25 mL) andbrine (25 mL), dried over MgSO₄, and concentrated. The residue waspurified by column chromatography through 24 g of silica gel eluted witha gradient of hexanes/ethyl acetate (9:1 to 1:1) to give the titlecompound as a white solid (3.25 g).

¹H NMR δ 6.54 (m, 2H), 3.88 (s, 3H), 3.83 (s, 3H), 2.16 (s, 3H).

Step E: Preparation of4-(2,6-Difluoro-4-methoxyphenyl)-1,3-dimethyl-N-(2,4,6-trifluorophenyl)-1H-pyrazol-5-amine

5-Bromo-4-(2,6-difluoro-4-methoxyphenyl)-1,3-dimethyl-1H-pyrazole (i.e.the product of Step D) (0.30 g, 0.94 mmol), palladium(II) acetate (20mg, 0.090 mmol), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (0.11g, 0.19 mmol) and powdered potassium carbonate (2.6 g, 19 mmol) werecombined in anhydrous 1,4-dioxane (4 mL), and the resulting mixture wassparged with a subsurface stream of N₂ gas for 10 min.2,4,6-Trifluoroaniline (0.28 g, 1.9 mmol) was added in one portion, andthe reaction mixture was heated at reflux under nitrogen for 22 h. Thereaction mixture was cooled, then filtered through Celite® diatomaceousfilter aid. The filter pad was washed with ethyl acetate (20 mL), andthe filtrate was washed with water (10 mL) and brine (10 mL), dried overMgSO₄, and concentrated to leave a semisolid residue. The residue waspurified by column chromatography through 12 g of silica gel eluted witha gradient of hexanes/ethyl acetate (20:1 to 1:3) to give the titlecompound, a compound of the present invention, as a semisolid (73 mg).

¹H NMR (acetone-d₆) δ 6.84 (br s, 1H), 6.68 (m, 2H), 6.43 (m, 2H), 3.77(s, 3H), 3.75 (s, 3H), 1.99 (s, 3H). MS: 384 amu (AP⁺).

Synthesis Example 4 Preparation of4-[[4-(2-Chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-yl]oxy]-3,5-difluorobenzonitrile(Compound 45) Step A: Preparation of4-[(1,3-Dimethyl-1H-pyrazol-5-yl)oxy]-3,5-difluorobenzonitrile

Potassium carbonate (1.38 g, 10 mmol) was added to a solution of2,4-dihydro-2,5-dimethyl-3H-pyrazol-3-one (0.70 g, 6.3 mmol) inN,N-dimethylformamide (15 mL). 3,4,5-Trifluorobenzonitrile (0.94 g, 6.0mmol) was added, and the reaction mixture was heated at 75° C. under anitrogen atmosphere for 16 h, then allowed to cool. The reaction mixturewas partitioned between water (60 mL) and ethyl acetate (30 mL). Theorganic phase was washed with water (2×30 mL) and brine (30 mL), driedover MgSO₄, and concentrated to give the title compound as a yellow oil(1.38 g).

¹H NMR δ 7.36 (m, 2H), 5.24 (s, 1H), 3.78 (s, 3H), 2.16 (s, 3H).

Step B: Preparation of3,5-Difluoro-4-[(4-iodo-1,3-dimethyl-1H-pyrazol-5-yl)oxy]benzonitrile

A solution of4-[(1,3-dimethyl-1H-pyrazol-5-yl)oxy]-3,5-difluorobenzonitrile (i.e. theproduct of Step A) (1.38 g, 5.5 mmol) in acetonitrile (20 mL) wasstirred at ambient temperature, and N-iodosuccinimide (1.35 g, 6.0 mmol)was added in one portion. The reaction mixture was heated at reflux for2 h, cooled, and then poured into water (40 mL). The resulting mixturewas extracted with ethyl acetate (40 mL). The organic phase was washedwith water (20 mL) and saturated aqueous NaHCO₃ solution (20 mL), driedover MgSO₄, and concentrated under reduced pressure to give the titlecompound as a tan solid (2.1 g).

¹H NMR (acetone-d₆) δ 7.80 (m, 2H), 3.82 (s, 3H), 2.09 (s, 3H). MS: 376amu (AP⁺).

Step C: Preparation of4-[[4-(2-Chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-yl]oxy]-3,5-difluorobenzonitrile

To a solution of3,5-difluoro-4-[(4-iodo-1,3-dimethyl-1H-pyrazol-5-yl)oxy]-benzonitrile(i.e. the product of Step B) (1.0 g, 2.67 mmol) in 1,4-dioxane (6 mL)was added 2-chloro-4-fluorobenzeneboronic acid (alternatively namedB-(2-chloro-4-fluorophenyl)-boronic acid) (0.93 g, 5.33 mmol), dichloro(bis)triphenylphosphine palladium(II) (alternatively namedbis(triphenylphosphine)palladium(II) dichloride) (93 mg, 0.13 mmol),potassium carbonate (0.74 g, 5.33 mmol), and water (4 mL). The resultingmixture was heated at reflux for 5 h, allowed to cool, and partitionedbetween water (20 mL) and ethyl acetate (20 mL). The organic layer wasdried over MgSO₄ and concentrated. The residue was purified bychromatography on silica gel with a gradient of hexanes/ethyl acetate toobtain the title compound, a compound of the present invention, as anoff-white solid (110 mg).

¹H NMR δ 7.00-7.09 (m, 3H), 6.97 (m, 1H), 6.86 (m, 1H), 3.85 (s, 3H),2.02 (s, 3H).

Synthesis Example 5 Preparation of4-(2,4-Dichlorophenyl)-N-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine(Compound 69) Step A: Preparation ofα-Acetyl-2,4-dichloro-N-(2,4-difluorophenyl)benzeneethanethioamide

2,4-Difluorophenyl isothiocyanate (0.27 mL, 2.0 mmol) was added to astirred suspension of sodium hydride (60% in mineral oil) (112 mg, 2.8mmol) in anhydrous tetrahydrofuran (4 mL) cooled in an ice-water bathunder a nitrogen atmosphere. A solution of(2,4-dichlorophenyl)-2-propanone (570 mg, 2.8 mmol) in tetrahydrofuran(4 mL) was added dropwise over 5 min. The resultant yellow solution wasstirred at 5-10° C. for 1 h. Water (10 mL) was carefully added, and thereaction mixture was extracted with ethyl acetate (10 mL). The aqueousphase was acidified to pH 3 with 1 N aqueous HCl, then extracted withethyl acetate (20 mL). The organic extract was washed with water (10 mL)and brine (10 mL), dried over MgSO₄, and concentrated to leave a solid.The solid was triturated with hexanes/ethyl acetate (2:1), collected ona glass frit, and air-dried to give the title compound as a white solid(240 mg). MS: 373 amu (AP⁺).

Step B: Preparation of4-(2,4-Dichlorophenyl)-N-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine

Acetic acid (50 μL) and methylhydrazine (41 μL) were added to a stirredsuspension ofα-acetyl-2,4-dichloro-N-(2,4-difluorophenyl)benzeneethanethioamide (238mg, 0.64 mmol) in ethanol (4 mL). The reaction mixture was heated atreflux for 2 h and allowed to cool. Then the reaction mixture wasdiluted with ethyl acetate (10 mL) and washed with 1 N aqueous NaOH (10mL), water (10 mL) and brine (10 mL), dried over MgSO₄, and concentratedto leave a solid residue. The residue was purified by columnchromatography on 5 g of silica gel with a gradient of hexanes/ethylacetate (2:1 to 1:1) to give the title compound as a solid (170 mg).

¹H NMR δ 7.43 (s, 1H), 7.19 (m, 1H), 7.07 (m, 1H), 6.78 (m, 1H), 6.62(m, 1H), 6.37 (m, 1H), 5.22 (br s, 1H), 3.70 (s, 3H), 2.18 (s, 3H). MS:368 amu (AP⁺).

Synthesis Example 6 Preparation of4-(2-Chloro-4-fluorophenyl)-α-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazole-5-methanol(Compound 351)

5-Bromo-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole (i.e. theproduct of Synthesis Example 2, Step A) (0.25 g, 0.82 mmol) wasdissolved in anhydrous tetrahydrofuran (12 mL), and the mixture wascooled in a dry ice/acetone bath under a nitrogen atmosphere. Acyclohexane solution of n-butyllithium (2.0 M, 0.49 mL, 0.98 mmol) wasadded dropwise over 5 minutes. After 15 minutes, a solution of2,4-difluorobenzaldehyde (0.09 mL, 0.82 mmol) in anhydroustetrahydrofuran (3 mL) was added slowly dropwise, causing the darkred-colored solution to lighten to a yellow color. After 45 minutes, thereaction mixture was quenched by the addition of saturated aqueous NH₄Clsolution (˜20 mL) and allowed to warm to ambient temperature. Thismixture was extracted with ethyl acetate, and the organic phase waswashed with saturated aqueous NH₄Cl solution (25 mL) and with brine,dried over Na₂SO₄, and concentrated to leave a viscous residue. Thisresidue was purified by column chromatography through silica gel elutedwith a gradient of ethyl acetate in hexane (7% to 10%) to give the titleproduct, a compound of the present invention, as a white semi-solid (109mg).

¹H NMR δ 7.5 (m, 1H), 7.1 (m, 2H), 7.0 (m, 1H), 6.85 (m, 2H), 6.0 (br s,1H), 5.9 (s, 1H), 3.8 (s, 3H), 2.1 (s, 3H). MS: 367 amu (AP⁺).

Synthesis Example 7 Preparation of[4-(2-Chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-yl](2,4-difluorophenyl)methanone(Compound 370)

4-(2-Chloro-4-fluorophenyl)-α-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazole-5-methanol(i.e. the product of Synthesis Example 6) (90 mg, 0.25 mmol) wasdissolved in dichloromethane (8 mL), and pyridinium dichromate (113 mg,0.3 mmol) was added in one portion. The reaction mixture was stirred atambient temperature for 16 h, and then the reaction mixture waspartitioned between water (5 mL) and dichloromethane (5 mL). The organicphase was washed with additional water (5 mL) and with brine (5 mL),dried over Na₂SO₄ and concentrated under reduced pressure to give aviscous residue. This residue was purified by column chromatographythrough silica gel eluted with a gradient of ethyl acetate in hexane(25% to 30%) to give the title product, a compound of the presentinvention, as a pale yellow viscous oil (29 mg).

¹H NMR δ 7.94 (m, 1H), 7.32 (s, 1H), 7.27 (m, 1H), 7.03 (m, 1H), 6.95(m, 1H), 6.78 (m, 1H), 3.82 (s, 3H), 2.13 (s, 3H). MS: 365 amu (AP⁺).

Synthesis Example 8 Preparation of5-(2,6-Difluoro-4-nitrophenoxy)-1,3-dimethyl-4-(2,4,6-trifluorophenyl)-1H-pyrazole(Compound 54) Step A: Preparation of Methyl2,4,6-trifluorobenzeneacetate

A solution of 2,4,6-trifluorobenzeneacetic acid (5.00 g, 26.3 mmol) inmethanol (25 mL) was stirred at ambient temperature, and thionylchloride (6 mL, ˜3 eq.) was added dropwise, causing the temperature ofthe reaction mixture to reach 60° C. The reaction mixture was allowed tocool to ambient temperature and was stirred for 3 h. Water (25 mL) wasadded with ice cooling. The mixture was extracted with ethyl acetate(2×100 mL). The combined organic phases were washed with water (2×),with saturated aqueous sodium bicarbonate solution and with brine, anddried over MgSO₄. Concentration provided the title product as a clearoil (5.38 g).

¹H NMR δ 6.68 (m, 2H), 3.72 (s, 3H), 3.66 (s, 2H).

Step B: Preparation of Methyl α-acetyl-2,4,6-trifluorobenzeneacetate

To a commercially obtained tetrahydrofuran solution of lithiumbis(trimethyl-silyl)amide (1.0 M, 21.0 mL), stirred under a nitrogenatmosphere and cooled to an internal temperature of −65° C., was addeddropwise over 30 minutes a solution of methyl2,4,6-trifluorobenzeneacetate (i.e. the product of Step A) (2.04 g, 10.0mmol) dissolved in dry tetrahydrofuran (10 mL). The reaction mixture wasstirred for an additional 30 minutes, and then while maintaining the−65° C. temperature, a solution of freshly distilled acetyl chloride(0.80 mL, 11 mmol) in dry tetrahydrofuran (3 mL) was added dropwise. Thereaction mixture was allowed to warm slowly to ambient temperature, andthen water (30 mL) was added. The resultant mixture was extracted withethyl acetate (60 mL). The aqueous phase was acidified with 1 Nhydrochloric acid and extracted with ethyl acetate (60 mL). Only thefirst extract was retained, because thin layer chromatographic analysisshowed the second extract to contain apparent polar impurities besidesadditional desired product. The initial organic phase was further washedwith 1 N hydrochloric acid, water and brine, dried over MgSO₄, andconcentrated to provide the title product as a clear oil (1.86 g).

¹H NMR δ 6.69 (m, 2H), 3.7 (m, 1H and s, 3H), 1.87 (s, 3H); minorresonances at 13.2 ppm and 4.9 ppm indicated presence of enolictautomer.

Step C: Preparation of1,3-Dimethyl-4-(2,4,6-trifluorophenyl)-1H-pyrazol-5-ol

To a solution of methyl α-acetyl-2,4,6-trifluorobenzeneacetate (i.e. theproduct of Step B) (2.46 g, 10.0 mmol) in methanol (15 mL) was addedmethylhydrazine (0.665 mL, 12.5 mmol), and the mixture was stirred atambient temperature over 3 days. Aqueous citric acid solution (1 M, 10mL) was added, and then water (50 mL) was added. The mixture wasextracted with ethyl acetate (2×50 mL). The combined organic extractswere washed with water and with brine, dried over MgSO₄, andconcentrated to leave a yellow solid. This solid was suspended in asmall volume of ethyl acetate (about 5 mL), an equal volume of hexaneswas gradually added, and the suspension was stirred for 30 minutes. Thesolid component was collected on a glass frit, washed with smallportions of ethyl acetate/hexanes (1:1 and 1:2 v:v), and allowed to dryin air to provide a white solid (1.02 g). Evaporation of the motherliquor and treatment of the resultant residue with small volumes ofethyl acetate and hexanes as already described provided an additional0.13 g of solid containing the title product (1.15 g total). Analysis ofthe combined solids by LC/MS showed a primary component of mass 242(AP+) and a minor component, eluting later by reverse-phase LC, alsohaving a mass of 242 (AP+). The apparent ratio of components was 94:6.

¹H NMR (acetone-d₆) δ 6.95 (m, 2H), 3.52 (s, 3H), 1.98 (s, 3H);5-hydroxy resonance was not observed in this solvent.

Step D: Preparation of5-(2,6-Difluoro-4-nitrophenoxy)-1,3-dimethyl-4-(2,4,6-trifluorophenyl)-1H-pyrazole

1,3-Dimethyl-4-(2,4,6-trifluorophenyl)-1H-pyrazol-5-ol (i.e. the productof Step C) (0.310 g, 1.28 mmol), was combined with3,4,5-trifluoronitrobenzene (157 μL, 1.35 mmol) and potassium carbonatepowder (0.27 g, 2 mmol) in dry N,N-dimethylformamide (4 mL). Thismixture was stirred and heated at 80° C. for 45 minutes and then allowedto cool. The reaction mixture was diluted with water (10 mL) andextracted with ethyl acetate (2×10 mL). The organic phase was washedwith water and with brine, dried over MgSO₄, and concentrated to leave aviscous residue. This residue was purified by column chromatographythrough silica gel eluted with a gradient of ethyl acetate (30% to 100%)in hexane to give the title product, a compound of the presentinvention, as an off-white solid (209 mg).

¹H NMR δ 7.71 (m, 2H), 6.54 (m, 2H), 3.86 (s, 3H), 2.07 (s, 3H); 400 amu(AP⁺).

Synthesis Example 9 Preparation of4-[[1,3-Dimethyl-4-(2,4,6-trifluorophenyl)-1H-pyrazol-5-yl]oxy]-3,5-difluorobenzenamine(Compound 371)

5-(2,6-Difluoro-4-nitrophenoxy)-1,3-dimethyl-4-(2,4,6-trifluorophenyl)-1H-pyrazole(i.e. the product of Synthesis Example 8) (0.780 g, 1.95 mmol) wascombined with iron powder (325 mesh, 0.58 g, 10 mmol) and ammoniumchloride (64 mg, 1.2 mmol) in ethanol (27 mL) to which water (3 mL) hadbeen added. The mixture was heated at reflux for 1.25 h and then allowedto cool. The reaction mixture was diluted with an equal volume of ethylacetate and filtered through Celite filter aid. The filtrate was driedwith MgSO₄ and concentrated. Analysis by LC/MS showed the majorcomponent (93%) to have mass 370 amu (AP⁺). The residue was dissolved inanhydrous dimethyl sulfoxide (8 mL), and a commercial solution of sodiummethoxide in methanol (0.45 mL of 25% solution) was added. This solutionwas stirred under nitrogen and heated at reflux for 1 h. Additionalsodium methoxide/methanol solution (0.20 mL) was added, and heating wascontinued for an additional 30 minutes. The reaction mixture was allowedto cool, and it was then treated with aqueous citric acid solution (1 M,5 mL), diluted with water (50 mL) and extracted with ethyl acetate (2×25mL). The organic phase was washed with water (3×) and with brine, driedover MgSO₄, and concentrated to leave the title product, a compound ofthe present invention, as a viscous oil (0.52 g).

¹H NMR δ 6.29 (m, 2H), 5.95 (m, 2H), 3.80 (s, 3H), 3.75 (s, 3H),3.55-3.75 (br s, NH₂), 2.01 (s, 3H); 382 amu (AP+).

Synthesis Example 10 Preparation of5-(4-Chloro-2,6-difluorophenoxy)-4-(2,6-difluoro-4-methoxyphenyl)-1,3-dimethyl-1H-pyrazole(Compound 58)

Copper(I) chloride (56 mg, 0.42 mmol) was added to a solution of4-[[4-(2,6-difluoro-4-methoxyphenyl)-1,3-dimethyl-1H-pyrazol-5-yl]oxy]-3,5-difluorobenzenamine(prepared analogous to Synthesis Example 9) (132 mg, 0.346 mmol) inacetonitrile (5 mL). The stirred mixture was cooled using an ice-waterbath, and tert-butyl nitrite (90% technical grade, 72 μL) was addeddropwise. The reaction mixture was allowed to warm slowly to ambienttemperature and stirred at room temperature overnight, and then it washeated at reflux for 1 h. Hydrochloric acid (1 N, 5 mL) was added, andthe mixture was extracted with ethyl acetate (˜20 mL). The organic phasewas washed with brine, dried over MgSO₄, and concentrated. The residuewas purified by column chromatography through silica gel eluted with 20%ethyl acetate in hexane to give the title product, a compound of thepresent invention, as a viscous oil (45 mg).

¹H NMR δ 6.74 (m, 2H), 6.30 (m, 2H), 3.83 (s, 3H), 3.75 (s, 3H), 2.03(s, 3H); 401 amu (AP+).

By the procedures described herein together with methods known in theart, the compounds disclosed in the Tables that follow can be prepared.The following abbreviations are used in the Table which follows: Memeans methyl, Et means ethyl, n-Pr means n-propyl, c-Pr meanscyclopropyl, Ph means phenyl, OMe (or MeO) means methoxy, OEt (or EtO)means ethoxy, —CN means cyano, and —NO₂ means nitro.

TABLE 1

Q¹ is 2,6-di-F-Ph, and R² is Me. (R³)_(p) 2-F 3-F 4-F 2-Cl 3-Cl 4-Cl2-Br 3-Br 4-Br 2,4-di-F 2,6-di-F 2,4,6-tri-F 2,4,5-tri-F 2,3,5-tri-F2,3,6-tri-F 2-Cl-4-F 2-F-4-Cl 2,4-di-Cl 2,6-di-Cl 2,4,6-tri-Cl 2-Br-4-F2-I-4-F 2-Me-4-F 2-F-4-MeO 2-Cl-4-MeO 2-Br-4-MeO 2,6-di-F-4-MeO 2-F-4-CN2-Cl-4-CN 2-Br-4-CN 2,6-di-F-4-CN 2-Cl-4,5-di-F 2-Cl-4,6-di-F2-Br-4,5-di-F 2-Br-4,6-di-F 4-Cl-2,5-di-F 4-Cl-2,6-di-F 4-Br-2,5-di-F4-Br-2,6-di-F 2,4-di-Cl-6-F 2,6-di-Cl-4-F 2,6-di-Cl-4-MeO 2-CF₃-4-F 4-Me2,4-di-Me 2-F-4-Br 2-Cl-4-Br 2-Br-4-Cl 2-Br-4-F-6-Cl 2-Cl-4-Br-6-F

The present disclosure also includes Tables 2 through 84, each of whichis constructed the same as Table 1 above, except that the row heading inTable 1 (i.e. “Q¹ is 2,6-di-F-Ph, and R² is Me.”) is replaced with therespective row heading shown below. For Example, in Table 2 the rowheading is “Q¹ is 2,6-di-F-Ph, and R² is Cl.”, and (R³)_(p) is asdefined in Table 1 above. Thus, the first entry in Table 2 specificallydiscloses2-chloro-4-(2,6-difluorophenyl)-N-(2-fluorophenyl)-1-methyl-1H-pyrazol-5-amine.Tables 3 through 84 are constructed similarly.

Table Row Heading 2 Q¹ is 2,6-di-F—Ph, and R² is Cl. 3 Q¹ is2,6-di-F—Ph, and R² is Br. 4 Q¹ is 2,4-di-F—Ph, and R² is Me. 5 Q¹ is2,4-di-F—Ph, and R² is Cl. 6 Q¹ is 2,4-di-F—Ph, and R² is Br. 7 Q¹ is2,4,6-tri-F—Ph, and R² is Me. 8 Q¹ is 2,4,6-tri-F—Ph, and R² is Cl. 9 Q¹is 2,4,6-tri-F—Ph, and R² is Br. 10 Q¹ is 2,6-di-F-4-OMe—Ph, and R² isMe. 11 Q¹ is 2,6-di-F-4-OMe—Ph, and R² is Cl. 12 Q¹ is2,6-di-F-4-OMe—Ph, and R² is Br.  12A Q¹ is 2,6-di-F-4-OEt—Ph, and R² isMe.  12B Q¹ is 2,6-di-F-4-OEt—Ph, and R² is Cl.  12C Q¹ is2,6-di-F-4-OEt—Ph, and R² is Br. 13 Q¹ is 2,6-di-F-4-CN—Ph, and R² isMe. 14 Q¹ is 2,6-di-F-4-CN—Ph, and R² is Cl. 15 Q¹ is 2,6-di-F-4-CN—Ph,and R² is Br. 16 Q¹ is 2-Cl-4-F—Ph, and R² is Me. 17 Q¹ is 2-Cl-4-F—Ph,and R² is Cl. 18 Q¹ is 2-Cl-4-F—Ph, and R² is Br. 19 Q¹ is 2-Cl-6-F—Ph,and R² is Me. 20 Q¹ is 2-Cl-6-F—Ph, and R² is Cl. 21 Q¹ is 2-Cl-6-F-Ph,and R² is Br. 22 Q¹ is 2-Cl-4,6-di-F—Ph, and R² is Me. 23 Q¹ is2-Cl-4,6-di-F—Ph, and R² is Cl. 24 Q¹ is 2-Cl-4,6-di-F—Ph, and R² is Br.25 Q¹ is 4-Cl-2,6-di-F—Ph, and R² is Me. 26 Q¹ is 4-Cl-2,6-di-F—Ph, andR² is Cl. 27 Q¹ is 4-Cl-2,6-di-F—Ph, and R² is Br. 28 Q¹ is 2-Br-4-F—Ph,and R² is Me. 29 Q¹ is 2-Br-4-F—Ph, and R² is Cl. 30 Q¹ is 2-Br-4-F—Ph,and R² is Br. 31 Q¹ is 2-Br-6-F—Ph, and R² is Me. 32 Q¹ is 2-Br-6-F—Ph,and R² is Cl. 33 Q¹ is 2-Br-6-F—Ph, and R² is Br. 34 Q¹ is 2-Me-4-F—Ph,and R² is Me. 35 Q¹ is 2-Me-4-F—Ph, and R² is Cl. 36 Q¹ is 2-Me-4-F—Ph,and R² is Br. 37 Q¹ is 2-I-4-F—Ph, and R² is Me. 38 Q¹ is 2-I-4-F—Ph,and R² is Cl. 39 Q¹ is 2-I-4-F—Ph, and R² is Br. 40 Q¹ is 2-F—Ph, and R²is Me. 41 Q¹ is 2-F—Ph, and R² is Cl. 42 Q¹ is 2-F—Ph, and R² is Br. 43Q¹ is 2-Cl—Ph, and R² is Me. 44 Q¹ is 2-Cl—Ph, and R² is Cl. 45 Q¹ is2-Cl—Ph, and R² is Br. 46 Q¹ is 2-Br—Ph, and R² is Me. 47 Q¹ is 2-Br—Ph,and R² is Cl. 48 Q¹ is 2-Br—Ph, and R² is Br. 49 Q¹ is 2-F-4-Cl—Ph, andR² is Me. 50 Q¹ is 2-F-4-Cl—Ph, and R² is Cl. 51 Q¹ is 2-F-4-Cl—Ph, andR² is Br. 52 Q¹ is 2,4-di-Cl—Ph, and R² is Me. 53 Q¹ is 2,4-di-Cl—Ph,and R² is Cl. 54 Q¹ is 2,4-di-Cl—Ph, and R² is Br. 55 Q¹ is2,6-di-Cl—Ph, and R² is Me. 56 Q¹ is 2,6-di-Cl—Ph, and R² is Cl. 57 Q¹is 2,6-di-Cl—Ph, and R² is Br. 58 Q¹ is 2-F-4-MeO—Ph, and R² is Me. 59Q¹ is 2-F-4-MeO—Ph, and R² is Cl. 60 Q¹ is 2-F-4-MeO—Ph, and R² is Br. 60A Q¹ is 2-F-4-EtO—Ph, and R² is Me.  60B Q¹ is 2-F-4-EtO—Ph, and R²is Cl.  60C Q¹ is 2-F-4-EtO—Ph, and R² is Br. 61 Q¹ is 2-Cl-4-MeO—Ph,and R² is Me. 62 Q¹ is 2-Cl-4-MeO—Ph, and R² is Cl. 63 Q¹ is2-Cl-4-MeO—Ph, and R² is Br.  63A Q¹ is 2-Cl-4-EtO—Ph, and R² is Me. 63B Q¹ is 2-Cl-4-EtO—Ph, and R² is Cl.  63C Q¹ is 2-Cl-4-EtO—Ph, and R²is Br. 64 Q¹ is 2-Br-4-MeO—Ph, and R² is Me. 65 Q1 is 2-Br-4-MeO—Ph, andR² is Cl. 66 Q¹ is 2-Br-4-MeO—Ph, and R² is Br.  66A Q¹ is2-Br-4-EtO—Ph, and R² is Me.  66B Q¹ is 2-Br-4-EtO—Ph, and R² is Cl. 66C Q¹ is 2-Br-4-EtO—Ph, and R² is Br. 67 Q¹ is 2-F-4-CN—Ph, and R² isMe. 68 Q¹ is 2-F-4-CN—Ph, and R² is Cl. 69 Q¹ is 2-F-4-CN—Ph, and R² isBr. 70 Q¹ is 2-Cl-4-CN—Ph, and R² is Me. 71 Q¹ is 2-Cl-4-CN—Ph, and R²is Cl. 72 Q¹ is 2-Cl-4-CN—Ph, and R² is Br. 73 Q¹ is 2-Br-4-CN—Ph, andR² is Me. 74 Q¹ is 2-Br-4-CN—Ph, and R² is Cl. 75 Q¹ is 2-Br-4-CN—Ph,and R² is Br. 76 Q¹ is 2,5-di-Cl-3-pyridinyl, and R² is Me. 77 Q¹ is2,5-di-Cl-3-pyridinyl, and R² is Cl. 78 Q¹ is 2,5-di-Cl-3-pyridinyl, andR² is Br. 79 Q¹ is 2-Cl-3-thienyl, and R² is Me. 80 Q¹ is2-Cl-3-thienyl, and R² is Cl. 81 Q¹ is 2-Cl-3-thienyl, and R² is Br. 82Q¹ is 2,5-di-Cl-3-thienyl, and R² is Me. 83 Q¹ is 2,5-di-Cl-3-thienyl,and R² is Cl. 84 Q¹ is 2,5-di-Cl-3-thienyl, and R² is Br.

TABLE 85

Q¹ is 2,6-di-F-Ph, X is O, R¹ and R^(1a) are both H, and R² is Me.(R³)_(p) 4-F 4-C1 4-Br 2,4-di-F 2-Br-4-F 2,6-di-F 2,4-di-Cl 2,6-di-Cl2-Cl-4-F 2-F-4-Cl 2-F-4-Br 2-Br-6-F 2-Cl-4-Br 2-Br-4-Cl 2-I-4-F 2-F-4-I2-Cl-4,6-di-F 4-Cl-2,6-di-F 2-Br-4,6-di-F 4-Br-2,6-di-F 2-F-4-MeO2-Cl-4-MeO 2,6-di-F-4-MeO 2-F-4-CN 2-C1-4-CN 2-Br-4-CN 2,6-di-F-4-CN2-F-4-NO₂ 2-Cl-4-NO₂ 2-Br-4-NO₂ 2,5-di-F-4-CN 4-Cl-2,5-di-F2-Br-4,5-di-F 4-Br-2,5-di-F 2-Cl-4,5-di-F

The present disclosure also includes Tables 86 through 280, each ofwhich is constructed the same as Table 85 above, except that the rowheading in Table 85 (i.e. “Q¹ is 2,6-di-F-Ph, X is O, R¹ and R^(1a) areboth H, and R² is Me.”) is replaced with the respective row headingshown below. For Example, in Table 86 the row heading is “Q¹ is2,6-di-F-Ph, X is O, R¹ and R^(1a) are both H, and R² is Cl.” and(R³)_(p) is as defined in Table 85 above. Thus, the first entry in Table86 specifically discloses3-chloro-4-(2,6-difluorophenyl)-5-(4-fluorophenoxy)-1-methyl-1H-pyrazole.Tables 87 through 280 are constructed similarly.

Table Row Heading 86 Q¹ is 2,6-di-F—Ph, X is O, R¹ and R^(1a) are bothH, and R² is Cl. 87 Q¹ is 2,6-di-F—Ph, X is O, R¹ and R^(1a) are both H,and R² is Br. 88 Q¹ is 2,4-di-F—Ph, X is O, R¹ and R^(1a) are both H,and R² is Me. 89 Q¹ is 2,4-di-F—Ph, X is O, R¹ and R^(1a) are both H,and R² is Cl. 90 Q¹ is 2,4-di-F—Ph, X is O, R¹ and R^(1a) are both H,and R² is Br. 91 Q¹ is 2,4,6-tri-F—Ph, X is O, R¹ and R^(1a) are both H,and R² is Me. 92 Q¹ is 2,4,6-tri-F—Ph, X is O, R¹ and R^(1a) are both H,and R² is Cl. 93 Q¹ is 2,4,6-tri-F—Ph, X is O, R¹ and R^(1a) are both H,and R² is Br. 94 Q¹ is 2,6-di-F-4-OMe—Ph, X is O, R¹ and R^(1a) are bothH, and R² is Me. 95 Q¹ is 2,6-di-F-4-OMe—Ph, X is O, R¹ and R^(1a) areboth H, and R² is Cl. 96 Q¹ is 2,6-di-F-4-OMe—Ph, X is O, R¹ and R^(1a)are both H, and R² is Br.   96A Q¹ is 2,6-di-F-4-OEt—Ph, X is O, R¹ andR^(1a) are both H, and R² is Me.   96B Q¹ is 2,6-di-F-4-OEt—Ph, X is O,R¹ and R^(1a) are both H, and R² is Cl.   96C Q¹ is 2,6-di-F-4-OEt—Ph, Xis O, R¹ and R^(1a) are both H, and R² is Br. 97 Q¹ is 2,6-di-F-4-CN—Ph,X is O, R¹ and R^(1a) are both H, and R² is Me. 98 Q¹ is2,6-di-F-4-CN—Ph, X is O, R¹ and R^(1a) are both H, and R² is Cl. 99 Q¹is 2,6-di-F-4-CN—Ph, X is O, R¹ and R^(1a) are both H, and R² is Br. 100Q¹ is 2-Cl-4-F—Ph, X is O, R¹ and R^(1a) are both H, and R² is Me. 101Q¹ is 2-Cl-4-F—Ph, X is O, R¹ and R^(1a) are both H, and R² is Cl. 102Q¹ is 2-Cl-4-F—Ph, X is O, R¹ and R^(1a) are both H, and R² is Br. 103Q¹ is 2-Cl-6-F—Ph, X is O, R¹ and R^(1a) are both H, and R² is Me. 104Q¹ is 2-Cl-6-F—Ph, X is O, R¹ and R^(1a) are both H, and R² is Cl. 105Q¹ is 2-Cl-6-F—Ph, X is O, R¹ and R^(1a) are both H, and R² is Br. 106Q¹ is 2-Cl-4,6-di-F—Ph, X is O, R¹ and R^(1a) are both H, and R² is Me.107 Q¹ is 2-Cl-4,6-di-F—Ph, X is O, R¹ and R^(1a) are both H, and R² isCl. 108 Q¹ is 2-Cl-4,6-di-F—Ph, X is O, R¹ and R^(1a) are both H, and R²is Br. 109 Q¹ is 4-Cl-2,6-di-F—Ph, X is O, R¹ and R^(1a) are both H, andR² is Me. 110 Q¹ is 4-Cl-2,6-di-F—Ph, X is O, R¹ and R^(1a) are both H,and R² is Cl. 111 Q¹ is 4-Cl-2,6-di-F—Ph, X is O, R¹ and R^(1a) are bothH, and R² is Br. 112 Q¹ is 2-Br-4-F—Ph, X is O, R¹ and R^(1a) are bothH, and R² is Me. 113 Q¹ is 2-Br-4-F—Ph, X is O, R¹ and R^(1a) are bothH, and R² is Cl. 114 Q¹ is 2-Br-4-F—Ph, X is O, R¹ and R^(1a) are bothH, and R² is Br. 115 Q¹ is 2-Br-6-F—Ph, X is O, R¹ and R^(1a) are bothH, and R² is Me. 116 Q¹ is 2-Br-6-F—Ph, X is O, R¹ and R^(1a) are bothH, and R² is Cl. 117 Q¹ is 2-Br-6-F—Ph, X is O, R¹ and R^(1a) are bothH, and R² is Br. 118 Q¹ is 2-Me-4-F—Ph, X is O, R¹ and R^(1a) are bothH, and R² is Me. 119 Q¹ is 2-Me-4-F—Ph, X is O, R¹ and R^(1a) are bothH, and R² is Cl. 120 Q¹ is 2-Me-4-F—Ph, X is O, R¹ and R^(1a) are bothH, and R² is Br. 121 Q¹ is 2-I-4-F—Ph, X is O, R¹ and R^(1a) are both H,and R² is Me. 122 Q¹ is 2-I-4-F—Ph, X is O, R¹ and R^(1a) are both H,and R² is Cl. 123 Q¹ is 2-I-4-F—Ph, X is O, R¹ and R^(1a) are both H,and R² is Br. 124 Q¹ is 2-F—Ph, X is O, R¹ and R^(1a) are both H, and R²is Me. 125 Q¹ is 2-F—Ph, X is O, R¹ and R^(1a) are both H, and R² is Cl.126 Q¹ is 2-F—Ph, X is O, R¹ and R^(1a) are both H, and R² is Br. 127 Q¹is 2-Cl—Ph, X is O, R¹ and R^(1a) are both H, and R² is Me. 128 Q¹ is2-Cl—Ph, X is O, R¹ and R^(1a) are both H, and R² is Cl. 129 Q¹ is2-Cl—Ph, X is O, R¹ and R^(1a) are both H, and R² is Br. 130 Q¹ is2-Br—Ph, X is O, R¹ and R^(1a) are both H, and R² is Me. 131 Q¹ is2-Br—Ph, X is O, R¹ and R^(1a) are both H, and R² is Cl. 132 Q¹ is2-Br—Ph, X is O, R¹ and R^(1a) are both H, and R² is Br. 133 Q¹ is2-F-4-Cl—Ph, X is O, R¹ and R^(1a) are both H, and R² is Me. 134 Q¹ is2-F-4-Cl—Ph, X is O, R¹ and R^(1a) are both H, and R² is Cl. 135 Q¹ is2-F-4-Cl—Ph, X is O, R¹ and R^(1a) are both H, and R² is Br. 136 Q¹ is2,4-di-Cl—Ph, X is O, R¹ and R^(1a) are both H, and R² is Me. 137 Q¹is2,4-di-Cl—Ph, X is O, R¹ and R^(1a) are both H, and R² is Cl. 138 Q¹is 2,4-di-Cl—Ph, X is O, R¹ and R^(1a) are both H, and R² is Br. 139 Q¹is 2,6-di-Cl—Ph, X is O, R¹ and R^(1a) are both H, and R² is Me. 140 Q¹is 2,6-di-Cl—Ph, X is O, R¹ and R^(1a) are both H, and R² is Cl. 141 Q¹is 2,6-di-Cl—Ph, X is O, R¹ and R^(1a) are both H, and R² is Br. 142 Q¹is 2-F-4-MeO—Ph, X is O, R¹ and R^(1a) are both H, and R² is Me. 143 Q¹is 2-F-4-MeO—Ph, X is O, R¹ and R^(1a) are both H, and R² is Cl. 144 Q¹is 2-F-4-MeO—Ph, X is O, R¹ and R^(1a) are both H, and R² is Br.  144AQ¹ is 2-F-4-EtO—Ph, X is O, R¹ and R^(1a) are both H, and R² is Me. 144B Q¹ is 2-F-4-EtO—Ph, X is O, R¹ and R^(1a) are both H, and R² isCl.  144C Q¹ is 2-F-4-EtO—Ph, X is O, R¹ and R^(1a) are both H, and R²is Br. 145 Q¹ is 2-Cl-4-MeO—Ph, X is O, R¹ and R^(1a) are both H, and R²is Me. 146 Q¹ is 2-Cl-4-MeO—Ph, X is O, R¹ and R^(1a) are both H, and R²is Cl. 147 Q¹ is 2-Cl-4-MeO—Ph, X is O, R¹ and R^(1a) are both H, and R²is Br.  147A Q¹ is 2-Cl-4-EtO—Ph, X is O, R¹ and R^(1a) are both H, andR² is Me.  147B Q¹ is 2-Cl-4-EtO—Ph, X is O, R¹ and R^(1a) are both H,and R² is Cl.  147C Q¹ is 2-Cl-4-EtO—Ph, X is O, R¹ and R^(1a) are bothH, and R² is Br. 148 Q¹ is 2-Br-4-MeO—Ph, X is O, R¹ and R^(1a) are bothH, and R² is Me. 149 Q¹ is 2-Br-4-MeO—Ph, X is O, R¹ and R^(1a) are bothH, and R² is Cl. 150 Q¹ is 2-Br-4-MeO—Ph, X is O, R¹ and R^(1a) are bothH, and R² is Br.  150A Q¹ is 2-Br-4-EtO—Ph, X is O, R¹ and R^(1a) areboth H, and R² is Me.  150B Q¹ is 2-Br-4-EtO—Ph, X is O, R¹ and R^(1a)are both H, and R² is Cl.  150C Q¹ is 2-Br-4-EtO—Ph, X is O, R¹ andR^(1a) are both H, and R² is Br. 151 Q¹ is 2-F-4-CN—Ph, X is O, R¹ andR^(1a) are both H, and R² is Me. 152 Q¹ is 2-F-4-CN—Ph, X is O, R¹ andR^(1a) are both H, and R² is Cl. 153 Q¹ is 2-F-4-CN—Ph, X is O, R¹ andR^(1a) are both H, and R² is Br. 154 Q¹ is 2-Cl-4-CN—Ph, X is O, R¹ andR^(1a) are both H, and R² is Me. 155 Q¹ is 2-Cl-4-CN—Ph, X is O, R¹ andR^(1a) are both H, and R² is Cl. 156 Q¹ is 2-Cl-4-CN—Ph, X is O, R¹ andR^(1a) are both H, and R² is Br. 157 Q¹ is 2-Br-4-CN—Ph, X is O, R¹ andR^(1a) are both H, and R² is Me. 158 Q¹ is 2-Br-4-CN—Ph, X is O, R¹ andR^(1a) are both H, and R² is Cl. 159 Q¹ is 2-Br-4-CN—Ph, X is O, R¹ andR^(1a) are both H, and R² is Br. 160 Q¹ is 2,5-di-Cl-3-pyridinyl, X isO, R¹ and R^(1a) are both H, and R² is Me. 161 Q¹ is2,5-di-Cl-3-pyridinyl, X is O, R¹ and R^(1a) are both H, and R² is Cl.162 Q¹ is 2,5-di-Cl-3-pyridinyl, X is O, R¹ and R^(1a) are both H, andR² is Br. 163 Q¹ is 2-Cl-3-thienyl, X is O, R¹ and R^(1a) are both H,and R² is Me. 164 Q¹ is 2-Cl-3-thienyl, X is O, R¹ and R^(1a) are bothH, and R² is Cl. 165 Q¹ is 2-Cl-3-thienyl, X is O, R¹ and R^(1a) areboth H, and R² is Br. 166 Q¹ is 2,5-di-Cl-3-thienyl, X is O, R¹ andR^(1a) are both H, and R² is Me. 167 Q¹ is 2,5-di-Cl-3-thienyl, X is O,R¹ and R^(1a) are both H, and R² is Cl. 168 Q¹ is 2,5-di-Cl-3-thienyl, Xis O, R¹ and R^(1a) are both H, and R² is Br. 169 Q¹ is 2,6-di-F—Ph, Xis S, R¹ and R^(1a) are both H, and R² is Me. 170 Q¹ is 2,6-di-F—Ph, Xis S, R¹ and R^(1a) are both H, and R² is Cl. 171 Q¹ is 2,6-di-F—Ph, Xis S, R¹ and R^(1a) are both H, and R² is Br. 172 Q¹ is 2,4-di-F—Ph, Xis S, R¹ and R^(1a) are both H, and R² is Me. 173 Q¹ is 2,4-di-F—Ph, Xis S, R¹ and R^(1a) are both H, and R² is Cl. 174 Q¹ is 2,4-di-F—Ph, Xis S, R¹ and R^(1a) are both H, and R² is Br. 175 Q¹ is 2,4,6-tri-F—Ph,X is S, R¹ and R^(1a) are both H, and R² is Me. 176 Q¹ is2,4,6-tri-F—Ph, X is S, R¹ and R^(1a) are both H, and R² is Cl. 177 Q¹is 2,4,6-tri-F—Ph, X is S, R¹ and R^(1a) are both H, and R² is Br. 178Q¹ is 2,6-di-F-4-OMe—Ph, X is S, R¹ and R^(1a) are both H, and R² is Me.179 Q¹ is 2,6-di-F-4-OMe—Ph, X is S, R¹ and R^(1a) are both H, and R² isCl. 180 Q¹ is 2,6-di-F-4-OMe—Ph, X is S, R¹ and R^(1a) are both H, andR² is Br.  180A Q¹ is 2,6-di-F-4-OEt—Ph, X is S, R¹ and R^(1a) are bothH, and R² is Me.  180B Q¹ is 2,6-di-F-4-OEt—Ph, X is S, R¹ and R^(1a)are both H, and R² is Cl.  180C Q¹ is 2,6-di-F-4-OEt—Ph, X is S, R¹ andR^(1a) are both H, and R² is Br. 181 Q¹ is 2,6-di-F-4-CN—Ph, X is S, R¹and R^(1a) are both H, and R² is Me. 182 Q¹ is 2,6-di-F-4-CN—Ph, X is S,R¹ and R^(1a) are both H, and R² is Cl. 183 Q¹ is 2,6-di-F-4-CN—Ph, X isS, R¹ and R^(1a) are both H, and R² is Br. 184 Q¹ is 2-Cl-4-F—Ph, X isS, R¹ and R^(1a) are both H, and R² is Me. 185 Q¹ is 2-Cl-4-F—Ph, X isS, R¹ and R^(1a) are both H, and R² is Cl. 186 Q¹ is 2-Cl-4-F—Ph, X isS, R¹ and R^(1a) are both H, and R² is Br. 187 Q¹ is 2-Cl-6-F—Ph, X isS, R¹ and R^(1a) are both H, and R² is Me. 188 Q¹ is 2-Cl-6-F—Ph, X isS, R¹ and R^(1a) are both H, and R² is Cl. 189 Q¹ is 2-Cl-6-F—Ph, X isS, R¹ and R^(1a) are both H, and R² is Br. 190 Q¹ is 2-Cl-4,6-di-F—Ph, Xis S, R¹ and R^(1a) are both H, and R² is Me. 191 Q¹ is2-Cl-4,6-di-F—Ph, X is S, R¹ and R^(1a) are both H, and R² is Cl. 192 Q¹is 2-Cl-4,6-di-F—Ph, X is S, R¹ and R^(1a) are both H, and R² is Br. 193Q¹ is 4-Cl-2,6-di-F—Ph, X is S, R¹ and R^(1a) are both H, and R² is Me.194 Q¹ is 4-Cl-2,6-di-F—Ph, X is S, R¹ and R^(1a) are both H, and R² isCl. 195 Q¹ is 4-Cl-2,6-di-F—Ph, X is S, R¹ and R^(1a) are both H, and R²is Br. 196 Q¹ is 2-Br-4-F—Ph, X is S, R¹ and R^(1a) are both H, and R²is Me. 197 Q¹ is 2-Br-4-F—Ph, X is S, R¹ and R^(1a) are both H, and R²is Cl. 198 Q¹ is 2-Br-4-F—Ph, X is S, R¹ and R^(1a) are both H, and R²is Br. 199 Q¹ is 2-Br-6-F—Ph, X is S, R¹ and R^(1a) are both H, and R²is Me. 200 Q¹ is 2-Br-6-F—Ph, X is S, R¹ and R^(1a) are both H, and R²is Cl. 201 Q¹ is 2-Br-6-F—Ph, X is S, R¹ and R^(1a) are both H, and R²is Br. 202 Q¹ is 2-Me-4-F—Ph, X is S, R¹ and R^(1a) are both H, and R²is Me. 203 Q¹ is 2-Me-4-F—Ph, X is S, R¹ and R^(1a) are both H, and R²is Cl. 204 Q¹ is 2-Me-4-F—Ph, X is S, R¹ and R^(1a) are both H, and R²is Br. 205 Q¹ is 2-I-4-F—Ph, X is S, R¹ and R^(1a) are both H, and R² isMe. 206 Q¹ is 2-I-4-F—Ph, X is S, R¹ and R^(1a) are both H, and R² isCl. 207 Q¹ is 2-I-4-F—Ph, X is S, R¹ and R^(1a) are both H, and R² isBr. 208 Q¹ is 2-F—Ph, X is S, R¹ and R^(1a) are both H, and R² is Me.209 Q¹ is 2-F—Ph, X is S, R¹ and R^(1a) are both H, and R² is Cl. 210 Q¹is 2-F—Ph, X is S, R¹ and R^(1a) are both H, and R² is Br. 211 Q¹ is2-Cl—Ph, X is S, R¹ and R^(1a) are both H, and R² is Me. 212 Q¹ is2-Cl—Ph, X is S, R¹ and R^(1a) are both H, and R² is Cl. 213 Q¹ is2-Cl—Ph, X is S, R¹ and R^(1a) are both H, and R² is Br. 214 Q¹ is2-Br—Ph, X is S, R¹ and R^(1a) are both H, and R² is Me. 215 Q¹ is2-Br—Ph, X is S, R¹ and R^(1a) are both H, and R² is Cl. 216 Q¹ is2-Br—Ph, X is S, R¹ and R^(1a) are both H, and R² is Br. 217 Q¹ is2-F-4-Cl—Ph, X is S, R¹ and R^(1a) are both H, and R² is Me. 218 Q¹ is2-F-4-Cl—Ph, X is S, R¹ and R^(1a) are both H, and R² is Cl. 219 Q¹ is2-F-4-Cl—Ph, X is S, R¹ and R^(1a) are both H, and R² is Br. 220 Q¹ is2,4-di-Cl—Ph, X is S, R¹ and R^(1a) are both H, and R² is Me. 221 Q¹ is2,4-di-Cl—Ph, X is S, R¹ and R^(1a) are both H, and R² is Cl. 222 Q¹ is2,4-di-Cl—Ph, X is S, R¹ and R^(1a) are both H, and R² is Br. 223 Q¹ is2,6-di-Cl—Ph, X is S, R¹ and R^(1a) are both H, and R² is Me. 224 Q¹ is2,6-di-Cl—Ph, X is S, R¹ and R^(1a) are both H, and R² is Cl. 225 Q¹ is2,6-di-Cl—Ph, X is S, R¹ and R^(1a) are both H, and R² is Br. 226 Q¹ is2-F-4-MeO—Ph, X is S, R¹ and R^(1a) are both H, and R² is Me. 227 Q¹ is2-F-4-MeO—Ph, X is S, R¹ and R^(1a) are both H, and R² is Cl. 228 Q¹ is2-F-4-MeO—Ph, X is S, R¹ and R^(1a) are both H, and R² is Br.  228A Q¹is 2-F-4-EtO—Ph, X is S, R¹ and R^(1a) are both H, and R² is Me.  228BQ¹ is 2-F-4-EtO—Ph, X is S, R¹ and R^(1a) are both H, and R² is Cl. 228C Q¹ is 2-F-4-EtO—Ph, X is S, R¹ and R^(1a) are both H, and R² isBr. 229 Q¹ is 2-Cl-4-MeO—Ph, X is S, R¹ and R^(1a) are both H, and R² isMe. 230 Q¹ is 2-Cl-4-MeO—Ph, X is S, R¹ and R^(1a) are both H, and R² isCl. 231 Q¹ is 2-Cl-4-MeO—Ph, X is S, R¹ and R^(1a) are both H, and R² isBr.  231A Q¹ is 2-Cl-4-EtO—Ph, X is S, R¹ and R^(1a) are both H, and R²is Me.  231B Q¹ is 2-Cl-4-EtO—Ph, X is S, R¹ and R^(1a) are both H, andR² is Cl.  231C Q¹ is 2-Cl-4-EtO—Ph, X is S, R¹ and R^(1a) are both H,and R² is Br. 232 Q¹ is 2-Br-4-MeO—Ph, X is S, R¹ and R^(1a) are both H,and R² is Me. 233 Q¹ is 2-Br-4-MeO—Ph, X is S, R¹ and R^(1a) are both H,and R² is Cl. 234 Q¹ is 2-Br-4-MeO—Ph, X is S, R¹ and R^(1a) are both H,and R² is Br.  234A Q¹ is 2-Br-4-EtO—Ph, X is S, R¹ and R^(1a) are bothH, and R² is Me.  234B Q¹ is 2-Br-4-EtO—Ph, X is S, R¹ and R^(1a) areboth H, and R² is Cl.  234C Q¹ is 2-Br-4-EtO—Ph, X is S, R¹ and R^(1a)are both H, and R² is Br. 235 Q¹ is 2-F-4-CN—Ph, X is S, R¹ and R^(1a)are both H, and R² is Me. 236 Q¹ is 2-F-4-CN—Ph, X is S, R¹ and R^(1a)are both H, and R² is Cl. 237 Q¹ is 2-F-4-CN—Ph, X is S, R¹ and R^(1a)are both H, and R² is Br. 238 Q¹ is 2-Cl-4-CN—Ph, X is S, R¹ and R^(1a)are both H, and R² is Me. 239 Q¹ is 2-Cl-4-CN—Ph, X is S, R¹ and R^(1a)are both H, and R² is Cl. 240 Q¹ is 2-Cl-4-CN—Ph, X is S, R¹ and R^(1a)are both H, and R² is Br. 241 Q¹ is 2-Br-4-CN—Ph, X is S, R¹ and R^(1a)are both H, and R² is Me. 242 Q¹ is 2-Br-4-CN—Ph, X is S, R¹ and R^(1a)are both H, and R² is Cl. 243 Q¹ is 2-Br-4-CN—Ph, X is S, R¹ and R^(1a)are both H, and R² is Br. 244 Q¹ is 2,5-di-Cl-3-pyridinyl, X is S, R¹and R^(1a) are both H, and R² is Me. 245 Q¹ is 2,5-di-Cl-3-pyridinyl, Xis S, R¹ and R^(1a) are both H, and R² is Cl. 246 Q¹ is2,5-di-Cl-3-pyridinyl, X is S, R¹ and R^(1a) are both H, and R² is Br.247 Q¹ is 2-Cl-3-thienyl, X is S, R¹ and R^(1a) are both H, and R² isMe. 248 Q¹ is 2-Cl-3-thienyl, X is S, R¹ and R^(1a) are both H, and R²is Cl. 249 Q¹ is 2-Cl-3-thienyl, X is S, R¹ and R^(1a) are both H, andR² is Br. 250 Q¹ is 2,5-di-Cl-3-thienyl, X is S, R¹ and R^(1a) are bothH, and R² is Me. 251 Q¹ is 2,5-di-Cl-3-thienyl, X is S, R¹ and R^(1a)are both H, and R² is Cl. 252 Q¹ is 2,5-di-Cl-3-thienyl, X is S, R¹ andR^(1a) are both H, and R² is Br. 253 Q¹ is 2,6-di-F—Ph, X is NH, R¹ andR^(1a) form c-Pr, and R² is Me. 254 Q¹ is is 2,4-di-F—Ph, X is O, R¹ isEt, R^(1a) is H, and R² is Cl. 255 Q¹ is is 2,4,6-tri-F—Ph, X is S, R¹and R^(1a) are both H, and R² is Et. 256 Q¹ is is 2,6-di-F-4-OMe—Ph, Xis CHOH, R¹ 257 Q¹ is is 2,6-di-F-4-CN—Ph, X is NH, R¹ is CH═CH2, R^(1a)is H, and R² is Cl. 258 Q¹ is 2-Cl-4-F—Ph, X is CHOH, X is O, R¹ isc-Pr, R^(1a) is H, and R² is Br. 259 Q¹ is 2-Cl-6-F—Ph, X is S, R¹ andR^(1a) form c-Pr, and R² is Me. 260 Q¹ is 2-Cl-4,6-di-F—Ph, X is CHOH,R¹ is c-Pr, R^(1a) is H, and R² is Cl. 261 Q¹ is 4-Cl-2,6-di-F—Ph, X isNH, X is NH, R¹ is Et, R^(1a) is H, and R² is Br. 262 Q¹ is 2-Br-4-F—Ph,X is O, R¹ and R^(1a) both H, and R² is Et. 263 Q¹ is 2-Br-6-F—Ph, X isS, R¹ is CH₂CH═CH₂, R^(1a) is H, and R² is Cl. 264 Q¹ is 2-Me-4-F—Ph, Xis CHOH, R¹ and R^(1a) are both H, and R ² is c-Pr. 265 Q¹ is2-1-4-F—Ph, X is NH, R¹ is CH₂CF₃, R^(1a) is H, and R² is Me. 266 Q¹ is2-F—Ph, X is O, R¹ is CH₂F, R^(1a) is H, and R² is Cl. 267 Q¹ is2-Cl—Ph, X is S, R¹ and R^(1a) are both H, and R² is CH₂Cl. 268 Q¹ is2-Br—Ph, X is CHCH₃, R¹ and R^(1a) are both H, and R² is Me. 269 Q¹ is2-F-4-Cl—Ph, X is C(CH₃)OH, R¹ and R^(1a) are both H, and R² is Me. 270Q¹ is 2,4-di-Cl—Ph, X is O, R¹ is Et, R^(1a) is H, and R² is Br. 271 Q¹is 2,6-di-Cl—Ph, X is S, R¹ and R^(1a) are both H, and R² is OMe. 272 Q¹is 2-F-4-MeO—Ph, X is CHOCH₃, R¹ and R^(1a) are both H, and R² is Cl.273 Q¹ is 2-Cl-4-MeO—Ph, X is NH, R¹ and R^(1a) form c-Pr, and R² is Br.274 Q¹ is 2-Br-4-MeO—Ph, X is O, R¹ is n-Pr, R^(1a) is H, and R² is Me.275 Q¹ is 2-F-4-CN—Ph, X is NH, R¹ is CH₂CCH, R^(1a) is H, and R² is Cl.276 Q¹ is 2-Cl-4-CN—Ph, X is C(OCH₃)₂, R¹ and R^(1a) are both H, and R²is Br. 277 Q¹ is 2-Br-4-CN—Ph, X is NH, R¹ and R^(1a) form c-Pr, and R²is Me. 278 Q¹ is 2,5-di-Cl-3-pyridinyl, X is O, R¹ is c-Pr, R^(1a) is H,and R² is Cl. 279 Q¹ is 2-Cl-3-thienyl, X is S, R¹ and R^(1a) are bothH, and R² is Et. 280 Q¹ is 2,5-di-Cl-3-thienyl, X is CHOH, R¹ is Et,R^(1a) is H, and R² is Me.

TABLE 281

Q¹ is 2,6-di-F-Ph, X is CHOH, and R² is Me. (R³)_(p) 4-F 4-Cl 4-Br 4-Me2,4-di-F 2,6-di-F 2,4-di-Cl 2,6-di-Cl 2-Cl-4-F 2-F-4-Cl 2-F-4-Br2-Br-6-F 2-Cl-4-Br 2-Br-4-Cl 2-I-4-F 2-F-4-I 2-Cl-4,6-di-F 4-Cl-2,6-di-F2-Br-4,6-di-F 4-Br-2,6-di-F 2-Br-4-F 2-Me-4-F 2,4,6-tri-F 2-Cl-4,5-di-F4-Cl-2,5-di-F 2-F-4-CN 2-C1-4-CN 2-Br-4-CN 2,6-diF-4-CN 2-F-4-MeO2-Cl-4-MeO 2-Br-4-MeO 2,6-di-F-4-MeO 4-Br-2,5-di-F 2-Br-4,5-di-F

The present disclosure also includes Tables 282 through 448, each ofwhich is constructed the same as Table 281 above, except that the rowheading in Table 281 (i.e. “Q¹ is 2,6-di-F-Ph, X is CHOH, and R² isMe.”) is replaced with the respective row heading shown below. ForExample, in Table 282 the row heading is “Q¹ is 2,6-di-F-Ph, X is CHOH,and R² is Cl.” and (R³)_(p) is as defined in Table 281 above. Thus, thefirst entry in Table 282 specifically discloses3-chloro-4-(2,6-difluorophenyl)-α-(4-fluorophenyl)-1-methyl-1H-pyrazole-5-methanol.Tables 283 through 448 are constructed similarly.

Table Row Heading 282 Q¹ is 2,6-di-F—Ph, X is CHOH, and R² is Cl. 283 Q¹is 2,6-di-F—Ph, X is CHOH, and R² is Br. 284 Q¹ is 2,4-di-F—Ph, X isCHOH, and R² is Me. 285 Q¹ is 2,4-di-F—Ph, X is CHOH, and R² is Cl. 286Q¹ is 2,4-di-F—Ph, X is CHOH, and R² is Br. 287 Q¹ is 2,4,6-tri-F—Ph, Xis CHOH, and R² is Me. 288 Q¹ is 2,4,6-tri-F—Ph, X is CHOH, and R² isCl. 289 Q¹ is 2,4,6-tri-F—Ph, X is CHOH, and R² is Br. 290 Q¹ is2,6-di-F-4-OMe—Ph, X is CHOH, and R² is Me. 291 Q¹ is 2,6-di-F-4-OMe—Ph,X is CHOH, and R² is Cl. 292 Q¹ is 2,6-di-F-4-OMe—Ph, X is CHOH, and R²is Br.  292A Q¹ is 2,6-di-F-4-OEt—Ph, X is CHOH, and R² is Me.  292B Q¹is 2,6-di-F-4-OEt—Ph, X is CHOH, and R² is Cl.  292C Q¹ is2,6-di-F-4-OEt—Ph, X is CHOH, and R² is Br. 293 Q¹ is 2,6-di-F-4-CN—Ph,X is CHOH, and R² is Me. 294 Q¹ is 2,6-di-F-4-CN—Ph, X is CHOH, and R²is Cl. 295 Q¹ is 2,6-di-F-4-CN—Ph, X is CHOH, and R² is Br. 296 Q¹ is2-Cl-4-F—Ph, X is CHOH, and R² is Me. 297 Q¹ is 2-Cl-4-F—Ph, X is CHOH,and R² is Cl. 298 Q¹ is 2-Cl-4-F—Ph, X is CHOH, and R² is Br. 299 Q¹ is2-Cl-6-F—Ph, X is CHOH, and R² is Me. 300 Q¹ is 2-Cl-6-F—Ph, X is CHOH,and R² is Cl. 301 Q¹ is 2-Cl-6-F—Ph, X is CHOH, and R² is Br. 302 Q¹ is2-Cl-4,6-di-F—Ph, X is CHOH, and R² is Me. 303 Q¹ is 2-Cl-4,6-di-F—Ph, Xis CHOH, and R² is Cl. 304 Q¹ is 2-Cl-4,6-di-F—Ph, X is CHOH, and R² isBr. 305 Q¹ is 4-Cl-2,6-di-F—Ph, X is CHOH, and R² is Me. 306 Q¹ is4-Cl-2,6-di-F—Ph, X is CHOH, and R² is Cl. 307 Q¹ is 4-Cl-2,6-di-F—Ph, Xis CHOH, and R² is Br. 308 Q¹ is 2-Br-4-F—Ph, X is CHOH, and R² is Me.309 Q¹ is 2-Br-4-F—Ph, X is CHOH, and R² is Cl. 310 Q¹ is 2-Br-4-F—Ph, Xis CHOH, and R² is Br. 311 Q¹ is 2-Br-6-F—Ph, X is CHOH, and R² is Me.312 Q¹ is 2-Br-6-F—Ph, X is CHOH, and R² is Cl. 313 Q¹ is 2-Br-6-F—Ph, Xis CHOH, and R² is Br. 314 Q¹ is 2-Me-4-F—Ph, X is CHOH, and R² is Me.315 Q¹ is 2-Me-4-F—Ph, X is CHOH, and R² is Cl. 316 Q¹ is 2-Me-4-F—Ph, Xis CHOH, and R² is Br. 317 Q¹ is 2-1-4-F—Ph, X is CHOH, and R² is Me.318 Q¹ is 2-1-4-F—Ph, X is CHOH, and R² is Cl. 319 Q¹ is 2-1-4-F—Ph, Xis CHOH, and R² is Br. 320 Q¹ is 2-F—Ph, X is CHOH, and R² is Me. 321 Q¹is 2-F—Ph, X is CHOH, and R² is Cl. 322 Q¹ is 2-F—Ph, X is CHOH, and R²is Br. 323 Q¹ is 2-Cl—Ph, X is CHOH, and R² is Me. 324 Q¹ is 2-Cl—Ph, Xis CHOH, and R² is Cl. 325 Q¹ is 2-Cl—Ph, X is CHOH, and R² is Br. 326Q¹ is 2-Br—Ph, X is CHOH, and R² is Me. 327 Q¹ is 2-Br—Ph, X is CHOH,and R² is Cl. 328 Q¹ is 2-Br—Ph, X is CHOH, and R² is Br. 329 Q¹ is2-F-4-Cl—Ph, X is CHOH, and R² is Me. 330 Q¹ is 2-F-4-Cl—Ph, X is CHOH,and R² is Cl. 331 Q¹ is 2-F-4-Cl—Ph, X is CHOH, and R² is Br. 332 Q¹ is2,4-di-Cl—Ph, X is CHOH, and R² is Me. 333 Q¹ is 2,4-di-Cl—Ph, X isCHOH, and R² is Cl. 334 Q¹ is 2,4-di-Cl—Ph, X is CHOH, and R² is Br. 335Q¹ is 2,6-di-Cl—Ph, X is CHOH, and R² is Me. 336 Q¹ is 2,6-di-Cl—Ph, Xis CHOH, and R² is Cl. 337 Q¹ is 2,6-di-Cl—Ph, X is CHOH, and R² is Br.338 Q¹ is 2-F-4-MeO—Ph, X is CHOH, and R² is Me. 339 Q¹ is 2-F-4-MeO—Ph,X is CHOH, and R² is Cl. 340 Q¹ is 2-F-4-MeO—Ph, X is CHOH, and R² isBr.  340A Q¹ is 2-F-4-EtO—Ph, X is CHOH, and R² is Me.  340B Q¹ is2-F-4-EtO—Ph, X is CHOH, and R² is Cl.  340C Q¹ is 2-F-4-EtO—Ph, X isCHOH, and R² is Br. 341 Q¹ is 2-Cl-4-MeO—Ph, X is CHOH, and R² is Me.342 Q¹ is 2-Cl-4-MeO—Ph, X is CHOH, and R² is Cl. 343 Q¹ is2-Cl-4-MeO—Ph, X is CHOH, and R² is Br.  343A Q¹ is 2-Cl-4-EtO—Ph, X isCHOH, and R² is Me.  343B Q¹ is 2-Cl-4-EtO—Ph, X is CHOH, and R² is Cl. 343C Q¹ is 2-Cl-4-EtO—Ph, X is CHOH, and R² is Br. 344 Q¹ is2-Br-4-MeO—Ph, X is CHOH, and R² is Me. 345 Q¹ is 2-Br-4-MeO—Ph, X isCHOH, and R² is Cl. 346 Q¹ is 2-Br-4-MeO—Ph, X is CHOH, and R² is Br. 346A Q¹ is 2-Br-4-EtO—Ph, X is CHOH, and R² is Me.  346B Q¹ is2-Br-4-EtO—Ph, X is CHOH, and R² is Cl.  346C Q¹ is 2-Br-4-EtO—Ph, X isCHOH, and R² is Br. 347 Q¹ is 2-F-4-CN—Ph, X is CHOH, and R² is Me. 348Q¹ is 2-F-4-CN—Ph, X is CHOH, and R² is Cl. 349 Q¹ is 2-F-4-CN—Ph, X isCHOH, and R² is Br. 350 Q¹ is 2-Cl-4-CN—Ph, X is CHOH, and R² is Me. 351Q¹ is 2-Cl-4-CN—Ph, X is CHOH, and R² is Cl. 352 Q¹ is 2-Cl-4-CN—Ph, Xis CHOH, and R² is Br. 353 Q¹ is 2-Br-4-CN—Ph, X is CHOH, and R² is Me.354 Q¹ is 2-Br-4-CN—Ph, X is CHOH, and R² is Cl. 355 Q¹ is 2-Br-4-CN—Ph,X is CHOH, and R² is Br. 356 Q¹ is 2,5-di-Cl-3-pyridinyl, X is CHOH, andR² is Me. 357 Q¹ is 2,5-di-Cl-3-pyridinyl, X is CHOH, and R² is Cl. 358Q¹ is 2,5-di-Cl-3-pyridinyl, X is CHOH, and R² is Br. 359 Q¹ is2-Cl-3-thienyl, X is CHOH, and R² is Me. 360 Q¹ is 2-Cl-3-thienyl, X isCHOH, and R² is Cl. 361 Q¹ is 2-Cl-3-thienyl, X is CHOH, and R² is Br.362 Q¹ is 2,5-di-Cl-3-thienyl, X is CHOH, and R² is Me. 363 Q¹ is2,5-di-Cl-3-thienyl, X is CHOH, and R² is Cl. 364 Q¹ is2,5-di-Cl-3-thienyl, X is CHOH, and R² is Br. 365 Q¹ is 2,6-di-F—Ph, Xis C(O), and R² is Cl. 366 Q¹ is 2,6-di-F—Ph, X is C(O), and R² is Cl.367 Q¹ is 2,6-di-F—Ph, X is C(O), and R² is Br. 368 Q¹ is 2,4-di-F—Ph, Xis C(O), and R² is Me. 369 Q¹ is 2,4-di-F—Ph, X is C(O), and R² is Cl.370 Q¹ is 2,4-di-F—Ph, X is C(O), and R² is Br. 371 Q¹ is2,4,6-tri-F—Ph, X is C(O), and R² is Me. 372 Q¹ is 2,4,6-tri-F—Ph, X isC(O), and R² is Cl. 373 Q¹ is 2,4,6-tri-F—Ph, X is C(O), and R² is Br.374 Q¹ is 2,6-di-F-4-OMe—Ph, X is C(O), and R² is Me. 375 Q¹ is2,6-di-F-4-OMe—Ph, X is C(O), and R² is Cl. 376 Q¹ is 2,6-di-F-4-OMe—Ph,X is C(O), and R² is Br.  376A Q¹ is 2,6-di-F-4-OEt—Ph, X is C(O), andR² is Me.  376B Q¹ is 2,6-di-F-4-OEt—Ph, X is C(O), and R² is Cl.  376CQ¹ is 2,6-di-F-4-OEt—Ph, X is C(O), and R² is Br. 377 Q¹ is2,6-di-F-4-CN—Ph, X is C(O), and R² is Me. 378 Q¹ is 2,6-di-F-4-CN—Ph, Xis C(O), and R² is Cl. 379 Q¹ is 2,6-di-F-4-CN—Ph, X is C(O), and R² isBr. 380 Q¹ is 2-Cl-4-F—Ph, X is C(O), and R² is Me. 381 Q¹ is2-Cl-4-F—Ph, X is C(O), and R² is Cl. 382 Q¹ is 2-Cl-4-F—Ph, X is C(O),and R² is Br. 383 Q¹ is 2-Cl-6-F—Ph, X is C(O), and R² is Me. 384 Q¹ is2-Cl-6-F—Ph, X is C(O), and R² is Cl. 385 Q¹ is 2-Cl-6-F—Ph, X is C(O),and R² is Br. 386 Q¹ is 2-Cl-4,6-di-F—Ph, X is C(O), and R² is Me. 387Q¹ is 2-Cl-4,6-di-F—Ph, X is C(O), and R² is Cl. 388 Q¹ is2-Cl-4,6-di-F—Ph, X is C(O), and R² is Br. 389 Q¹ is 4-Cl-2,6-di-F—Ph, Xis C(O), and R² is Me. 390 Q¹ is 4-Cl-2,6-di-F—Ph, X is C(O), and R² isCl. 391 Q¹ is 4-Cl-2,6-di-F—Ph, X is C(O), and R² is Br. 392 Q¹ is2-Br-4-F—Ph, X is C(O), and R² is Me. 393 Q¹ is 2-Br-4-F—Ph, X is C(O),and R² is Cl. 394 Q¹ is 2-Br-4-F—Ph, X is C(O), and R² is Br. 395 Q¹ is2-Br-6-F—Ph, X is C(O), and R² is Me. 396 Q¹ is 2-Br-6-F—Ph, X is C(O),and R² is Cl. 397 Q¹ is 2-Br-6-F—Ph, X is C(O), and R² is Br. 398 Q¹ is2-Me-4-F—Ph, X is C(O), and R² is Me. 399 Q¹ is 2-Me-4-F—Ph, X is C(O),and R² is Cl. 400 Q¹ is 2-Me-4-F—Ph, X is C(O), and R² is Br. 401 Q¹ is2-I-4-F—Ph, X is C(O), and R² is Me. 402 Q¹ is 2-I-4-F—Ph-Ph, X is C(O),and R² is Cl. 403 Q¹ is 2-I-4-F—Ph, X is C(O), and R² is Br. 404 Q¹ is2-F—Ph, X is C(O), and R² is Me. 405 Q¹ is 2-F—Ph, X is C(O), and R² isCl. 406 Q¹ is 2-F—Ph, X is C(O), and R² is Br. 407 Q¹ is 2-Cl—Ph, X isC(O), and R² is Me. 408 Q¹ is 2-Cl—Ph, X is C(O), and R² is Cl. 409 Q¹is 2-Cl—Ph, X is C(O), and R² is Br. 410 Q¹ is 2-Br—Ph, X is C(O), andR² is Me. 411 Q¹ is 2-Br—Ph, X is C(O), and R² is Cl. 412 Q¹ is 2-Br—Ph,X is C(O), and R² is Br. 413 Q¹ is 2-F-4-Cl—Ph, X is C(O), and R² is Me.414 Q¹ is 2-F-4-Cl—Ph, X is C(O), and R² is Cl. 415 Q¹ is 2-F-4-Cl—Ph, Xis C(O), and R² is Br. 416 Q¹ is 2,4-di-Cl—Ph, X is C(O), and R² is Me.417 Q¹ is 2,4-di-Cl—Ph, X is C(O), and R² is Cl. 418 Q¹ is 2,4-di-Cl—Ph,X is C(O), and R² is Br. 419 Q¹ is 2,6-di-Cl—Ph, X is C(O), and R² isMe. 420 Q¹ is 2,6-di-Cl—Ph, X is C(O), and R² is Cl. 421 Q¹ is2,6-di-Cl—Ph, X is C(O), and R² is Br. 422 Q¹ is 2-F-4-MeO—Ph, X isC(O), and R² is Me. 423 Q¹ is 2-F-4-MeO—Ph, X is C(O), and R² is Cl. 424Q¹ is 2-F-4-MeO—Ph, X is C(O), and R² is Br.  424A Q¹ is 2-F-4-EtO—Ph, Xis C(O), and R² is Me.  424B Q¹ is 2-F-4-EtO—Ph, X is C(O), and R² isCl.  424C Q¹ is 2-F-4-EtO—Ph, X is C(O), and R² is Br. 425 Q¹ is2-Cl-4-MeO—Ph, X is C(O), and R² is Me. 426 Q¹ is 2-Cl-4-MeO—Ph, X isC(O), and R² is Cl. 427 Q¹ is 2-Cl-4-MeO—Ph, X is C(O), and R² is Br. 427A Q¹ is 2-Cl-4-EtO—Ph, X is C(O), and R² is Me.  427B Q¹ is2-Cl-4-EtO—Ph, X is C(O), and R² is Cl.  427C Q¹ is 2-Cl-4-EtO—Ph, X isC(O), and R² is Br. 428 Q¹ is 2-Br-4-MeO—Ph, X is C(O), and R² is Me.429 Q¹ is 2-Br-4-MeO—Ph, X is C(O), and R² is Cl. 430 Q¹ is2-Br-4-MeO—Ph, X is C(O), and R² is Br.  430A Q¹ is 2-Br-4-EtO—Ph, X isC(O), and R² is Me.  430B Q¹ is 2-Br-4-EtO—Ph, X is C(O), and R² is Cl. 430C Q¹ is 2-Br-4-EtO—Ph, X is C(O), and R² is Br. 431 Q¹ is2-F-4-CN—Ph, X is C(O), and R² is Me. 432 Q¹ is 2-F-4-CN—Ph, X is C(O),and R² is Cl. 433 Q¹ is 2-F-4-CN—Ph, X is C(O), and R² is Br. 434 Q¹ is2-Cl-4-CN—Ph, X is C(O), and R² is Me. 435 Q¹ is 2-Cl-4-CN—Ph, X isC(O), and R² is Cl. 436 Q¹ is 2-Cl-4-CN—Ph, X is C(O), and R² is Br. 437Q¹ is 2-Br-4-CN—Ph, X is C(O), and R² is Me. 438 Q¹ is 2-Br-4-CN—Ph, Xis C(O), and R² is Cl. 439 Q¹ is 2-Br-4-CN—Ph, X is C(O), and R² is Br.440 Q¹ is 2,5-di-Cl-3-pyridinyl, X is C(O), and R² is Me. 441 Q¹ is2,5-di-Cl-3-pyridinyl, X is C(O), and R² is Cl. 442 Q¹ is2,5-di-Cl-3-pyridinyl, X is C(O), and R² is Br. 443 Q¹ is2-Cl-3-thienyl, X is C(O), and R² is Me. 444 Q¹ is 2-Cl-3-thienyl, X isC(O), and R² is Cl. 445 Q¹ is 2-Cl-3-thienyl, X is C(O), and R² is Br.446 Q¹ is 2,5-di-Cl-3-thienyl, X is C(O), and R² is Me. 447 Q¹ is2,5-di-Cl-3-thienyl, X is C(O), and R² is Cl. 448 Q¹ is2,5-di-Cl-3-thienyl, X is C(O), and R² is Br.

TABLE 449

Q² Q² Q² Q² 2-Cl-3-pyridinyl 6-Cl-3-pyridinyl 2,6-di-Cl-3-pyridinyl3-Cl-2-pyridinyl 3,5-di-Cl-2-pyridinyl 3,5-di-F-2-pyridinyl5-Me-2-pyridinyl 5-CN-2-pyridinyl 5-pyrimidinyl 2-Cl-5-pyrimidinyl1,3-di-Me-5-pyrazolyl 5-Me-2-thiazolyl 5-Cl-2-pyridinyl3,5-di-Cl-4-pyridinyl tetrahydro-2H-pyran-4-yl quinolin-2-yl Q¹ is2,6-di-F—Ph, and X is NH.

The present disclosure also includes Tables 450 through 587, each ofwhich is constructed the same as Table 449 above, except that the rowheading in Table 449 (i.e. “Q¹ is 2,6-di-F-Ph, and X is NH.”) isreplaced with the respective row heading shown below. For Example, inTable 450 the row heading is “Q¹ is 2,4-di-F-Ph, and X is NH.” and Q² isas defined in Table 449 above. Thus, the first entry in Table 450specifically discloses2-chloro-N-[4-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-yl]-3-pyridinamine.Tables 451 through 587 are constructed similarly.

Table Row Heading 450 Q¹ is 2,4-di-F-Ph, and X is NH. 451 Q¹ is2,4,6-tri-F-Ph, and X is NH. 452 Q¹ is 2,6-di-F-4-OMe-Ph, and X is NH.453 Q¹ is 2,6-di-F-4-CN-Ph, and X is NH. 454 Q¹ is 2-Cl-4-F-Ph, and X isNH. 455 Q¹ is 2-Cl-6-F-Ph, and X is NH. 456 Q¹ is 2-Cl-4,6-di-F-Ph, andX is NH. 457 Q¹ is 4-Cl-2,6-di-F-Ph, and X is NH. 458 Q¹ is 2-Br-4-F-Ph,and X is NH. 459 Q¹ is 2-Br-6-F-Ph, and X is NH. 460 Q¹ is 2-Me-4-F-Ph,and X is NH. 461 Q¹ is 2-I-4-F-Ph, and X is NH. 462 Q¹ is 2-F-Ph, and Xis NH. 463 Q¹ is 2-Cl-Ph, and X is NH. 464 Q¹ is 2-Br-Ph, and X is NH.465 Q¹ is 2-F-4-Cl-Ph, and X is NH. 466 Q¹ is 2,4-di-Cl-Ph, and X is NH.467 Q¹ is 2,6-di-Cl-Ph, and X is NH. 468 Q¹ is 2-F-4-MeO-Ph, and X isNH. 469 Q¹ is 2-Cl-4-MeO-Ph, and X is NH. 470 Q¹ is 2-Br-4-MeO-Ph, and Xis NH. 471 Q¹ is 2-F-4-CN-Ph, and X is NH. 472 Q¹ is 2-Cl-4-CN-Ph, and Xis NH. 473 Q¹1 is 2-Br-4-CN-Ph, and X is NH. 474 Q¹ is2,5-di-Cl-3-pyridinyl, and X is NH. 475 Q¹ is 2-Cl-3-thienyl, and X isNH. 476 Q¹ is 2,5-di-Cl-3-thienyl, and X is NH. 477 Q¹ is 2,6-di-F-Ph,and X is O. 478 Q¹ is 2,4-di-F-Ph, and X is O. 479 Q¹ is 2,4,6-tri-F-Ph,and X is O. 480 Q¹ is 2,6-di-F-4-OMe-Ph, and X is O. 481 Q¹ is2,6-di-F-4-CN-Ph, and X is O. 482 Q¹ is 2-Cl-4-F-Ph, and X is O. 483 Q¹is 2-Cl-6-F-Ph, and X is O. 484 Q¹ is 2-Cl-4,6-di-F-Ph, and X is O. 485Q¹ is 4-Cl-2,6-di-F-Ph, and X is O. 486 Q¹ is 2-Br-4-F-Ph, and X is O.487 Q¹ is 2-Br-6-F-Ph, and X is O. 488 Q¹ is 2-Me-4-F-Ph, and X is O.489 Q¹ is 2-I-4-F-Ph, and X is O. 490 Q¹ is 2-F-Ph, and X is O. 491 Q¹is 2-Cl-Ph, and X is O. 492 Q¹ is 2-Br-Ph, and X is O. 493 Q¹ is2-F-4-Cl-Ph, and X is O. 494 Q¹ is 2,4-di-Cl-Ph, and X is O. 495 Q¹ is2,6-di-Cl-Ph, and X is O. 496 Q¹ is 2-F-4-MeO-Ph, and X is O. 497 Q¹ is2-Cl-4-MeO-Ph, and X is O. 498 Q¹ is 2-Br-4-MeO-Ph, and X is O. 499 Q¹is 2-F-4-CN-Ph, and X is O. 500 Q¹ is 2-Cl-4-CN-Ph, and X is O. 501 Q¹is 2-Br-4-CN-Ph, and X is O. 502 Q¹ is 2,5-di-Cl-pyridin-3-yl, and X isO. 503 Q¹ is 2-Cl-thien-3-yl, and X is O. 504 Q¹ is2,5-di-Cl-thien-3-yl, and X is O. 505 Q¹ is 2,6-di-F-Ph, and X is S. 506Q¹ is 2,4-di-F-Ph, and X is S. 507 Q¹ is 2,4,6-tri-F-Ph, and X is S. 508Q¹ is 2,6-di-F-4-OMe-Ph, and X is S. 509 Q¹ is 2,6-di-F-4-CN-Ph, and Xis S. 510 Q¹ is 2-Cl-4-F-Ph, and X is S. 511 Q¹ is 2-Cl-6-F-Ph, and X isS. 512 Q¹ is 2-Cl-4,6-di-F-Ph, and X is S. 513 Q¹ is 4-Cl-2,6-di-F-Ph,and X is S. 514 Q¹ is 2-Br-4-F-Ph, and X is S. 515 Q¹ is 2-Br-6-F-Ph,and X is S. 516 Q¹ is 2-Me-4-F-Ph, and X is S. 517 Q¹ is 2-I-4-F-Ph, andX is S. 518 Q¹ is 2-F-Ph, and X is S. 519 Q¹ is 2-Cl-Ph, and X is S. 520Q¹ is 2-Br-Ph, and X is S. 521 Q¹ is 2-F-4-Cl-Ph, and X is S. 522 Q¹ is2,4-di-Cl-Ph, and X is S. 523 Q¹ is 2,6-di-Cl-Ph, and X is S. 524 Q¹ is2-F-4-MeO-Ph, and X is S. 525 Q¹ is 2-Cl-4-MeO-Ph, and X is S. 526 Q¹ is2-Br-4-MeO-Ph, and X is S. 527 Q¹ is 2-F-4-CN-Ph, and X is S. 528 Q¹ is2-Cl-4-CN-Ph, and X is S. 529 Q¹ is 2-Br-4-CN-Ph, and X is S. 530 Q¹ is2,5-di-Cl-3-pyridinyl, and X is S. 531 Q¹ is 2-Cl-3-thienyl, and X is S.532 Q¹ is 2,5-di-Cl-3-thienyl, and X is S. 533 Q¹ is 2,6-di-F-Ph, and Xis CHOH. 534 Q¹ is 2,4-di-F-Ph, and X is CHOH. 535 Q¹ is 2,4,6-tri-F-Ph,and X is CHOH. 536 Q¹ is 2,6-di-F-4-OMe-Ph, and X is CHOH. 537 Q¹ is2,6-di-F-4-CN-Ph, and X is CHOH. 538 Q¹ is 2-Cl-4-F-Ph, and X is CHOH.539 Q¹ is 2-Cl-6-F-Ph, and X is CHOH. 540 Q¹ is 2-Cl-4,6-di-F-Ph, and Xis CHOH. 541 Q¹ is 4-Cl-2,6-di-F-Ph, and X is CHOH. 542 Q¹ is2-Br-4-F-Ph, and X is CHOH. 543 Q¹ is 2-Br-6-F-Ph, and X is CHOH. 544 Q¹is 2-Me-4-F-Ph, and X is CHOH. 545 Q¹ is 2-I-4-F-Ph, and X is CHOH. 546Q¹ is 2-F-Ph, and X is CHOH. 547 Q¹ is 2-Cl-Ph, and X is CHOH. 548 Q¹ is2-Br-Ph, and X is CHOH. 549 Q¹ is 2-F-4-Cl-Ph, and X is CHOH. 550 Q¹ is2,4-di-Cl-Ph, and X is CHOH. 551 Q¹ is 2,6-di-Cl-Ph, and X is CHOH. 552Q¹ is 2-F-4-MeO-Ph, and X is CHOH. 553 Q¹ is 2-Cl-4-MeO-Ph, and X isCHOH. 554 Q¹ is 2-Br-4-MeO-Ph, and X is CHOH. 555 Q¹ is 2-F-4-CN-Ph, andX is CHOH. 556 Q¹ is 2-Cl-4-CN-Ph, and X is CHOH. 557 Q¹ is2-Br-4-CN-Ph, and X is CHOH. 558 Q¹ is 2,5-di-Cl-pyridin-3-yl, and X isCHOH. 559 Q¹ is 2,5-di-Cl-thien-3-yl, and X is CHOH. 560 Q¹ is2,6-di-F-Ph, and X is C(O). 561 Q¹ is 2,4-di-F-Ph, and X is C(O). 562 Q¹is 2,4,6-tri-F-Ph, and X is C(O). 563 Q¹ is 2,6-di-F-4-OM-Ph e, and X isC(O). 564 Q¹ is 2,6-di-F-4-CN-Ph, and X is C(O). 565 Q¹ is 2-Cl-4-F-Ph,and X is C(O). 566 Q¹ is 2-Cl-6-F-Ph, and X is C(O). 567 Q¹ is2-Cl-4,6-di-F-Ph, and X is C(O). 568 Q¹ is 4-Cl-2,6-di-F-Ph, and X isC(O). 569 Q¹ is 2-Br-4-F-Ph, and X is C(O). 570 Q¹ is 2-Br-6-F-Ph, and Xis C(O). 571 Q¹ is 2-Me-4-F-Ph, and X is C(O). 572 Q¹ is 2-I-4-F-Ph, andX is C(O). 573 Q¹ is 2-F-Ph, and X is C(O). 574 Q¹ is 2-Cl-Ph, and X isC(O). 575 Q¹ is 2-Br-Ph, and X is C(O). 576 Q¹ is 2-F-4-Cl-Ph, and X isC(O). 577 Q¹ is 2,4-di-Cl-Ph, and X is C(O). 578 Q¹ is 2,6-di-Cl-Ph, andX is C(O). 579 Q¹ is 2-F-4-MeO-Ph, and X is C(O). 580 Q¹ is2-Cl-4-MeO-Ph, and X is C(O). 581 Q¹ is 2-Br-4-MeO-Ph, and X is C(O).582 Q¹ is 2-F-4-CN-Ph, and X is C(O). 583 Q¹ is 2-Cl-4-CN-Ph, and X isC(O). 584 Q¹ is 2-Br-4-CN-Ph, and X is C(O). 585 Q¹ is2,5-di-Cl-3-pyridinyl, and X is C(O). 586 Q¹ is 2-Cl-3-thienyl, and X isC(O). 587 Q¹ is 2,5-di-Cl-3-thienyl, and X is C(O).

TABLE 588

(R³)_(p) (R³)_(p) (R³)_(p) (R³)_(p) (R³)_(p) 2-F 3-F 4-F 2-Cl 3-Cl 4-Cl2-Br 3-Br 4-Br 2,4-di-F 2,6-di-F 2,4,6-tri-F 2,4,5-tri-F 2,3,5-tri-F2,3,6-tri-F 2-Cl-4-F 2-F-4-Cl 2,4-di-Cl 2,6-di-Cl 2,4,6-tri-Cl 2-Br-4-F2-I-4-F 2-Me-4-F 2-F-4-MeO 2-Cl-4-MeO 2-Br-4-MeO 2,6-di-F-4-MeO 2-F-4-CN2-Cl-4-CN 2-Br-4-CN 2,6-di-F-4-CN 2-Cl-4,5-di-F 2-Cl-4,6-di-F2-Br-4,5-di-F 2-Br-4,6-di-F 4-Cl-2,5-di-F 4-Cl-2,6-di-F 4-Br-2,5-di-F4-Br-2,6-di-F 2,4-di-Cl-6-F 2,6-di-Cl-4-F 2,6-di-Cl-4-MeO 2-CF₃-4-F 4-Me2,4-di-Me 2-F-4-Br 2-Cl-4-Br 2-Br-4-Cl 2-Br-4-F-6-Cl 2-Cl-4-Br-6-F Q¹is2,6-di-F—Ph, and R² is Me.

The present disclosure also includes Tables 589 through 671, each ofwhich is constructed the same as Table 588 above, except that the rowheading in Table 588 (i.e. “Q¹ is 2,6-di-F-Ph, and R² is Me.”) isreplaced with the respective row heading shown below. For Example, inTable 589 the row heading is “Q¹ is 2,6-di-F-Ph, and R² is Cl.”, and(R³)_(p) is as defined in Table 588 above. Thus, the first entry inTable 589 specifically discloses5-chloro-4-(2,6-difluorophenyl)-N-(2-fluorophenyl)-1H-pyrazol-3-amine.Tables 589 through 671 are constructed similarly.

Table Row Heading 589 Q¹ is 2,6-di-F-Ph, and R² is Cl. 590 Q¹ is2,6-di-F-Ph, and R² is Br. 591 Q¹ is 2,4-di-F-Ph, and R² is Me. 592 Q¹is 2,4-di-F-Ph, and R² is Cl. 593 Q¹ is 2,4-di-F-Ph, and R² is Br. 594Q¹ is 2,4,6-tri-F-Ph, and R² is Me. 595 Q¹ is 2,4,6-tri-F-Ph, and R² isCl. 596 Q¹ is 2,4,6-tri-F-Ph, and R² is Br. 597 Q¹ is 2,6-di-F-4-OMe-Ph,and R² is Me. 598 Q¹ is 2,6-di-F-4-OMe-Ph, and R² is Cl. 599 Q¹ is2,6-di-F-4-OMe-Ph, and R² is Br. 599A Q¹ is 2,6-di-F-4-OEt-Ph, and R² isMe. 599B Q¹ is 2,6-di-F-4-OEt-Ph, and R² is Cl. 599C Q¹ is2,6-di-F-4-OEt-Ph, and R² is Br. 600 Q¹ is 2,6-di-F-4-CN-Ph, and R² isMe. 601 Q¹ is 2,6-di-F-4-CN-Ph, and R² is Cl. 602 Q¹ is2,6-di-F-4-CN-Ph, and R² is Br. 603 Q¹ is 2-Cl-4-F-Ph, and R² is Me. 604Q¹ is 2-Cl-4-F-Ph, and R² is Cl. 605 Q¹ is 2-Cl-4-F-Ph, and R² is Br.606 Q¹ is 2-Cl-6-F-Ph, and R² is Me. 607 Q¹ is 2-Cl-6-F-Ph, and R² isCl. 608 Q¹ is 2-Cl-6-F-Ph, and R² is Br. 609 Q¹ is 2-Cl-4,6-di-F-Ph, andR² is Me. 610 Q¹ is 2-Cl-4,6-di-F-Ph, and R² is Cl. 611 Q¹ is2-Cl-4,6-di-F-Ph, and R² is Br. 612 Q¹ is 4-Cl-2,6-di-F-Ph, and R² isMe. 613 Q¹ is 4-Cl-2,6-di-F-Ph, and R² is Cl. 614 Q¹ is4-Cl-2,6-di-F-Ph, and R² is Br. 615 Q¹ is 2-Br-4-F-Ph, and R² is Me. 616Q¹ is 2-Br-4-F-Ph, and R² is Cl. 617 Q¹ is 2-Br-4-F-Ph, and R² is Br.618 Q¹ is 2-Br-6-F-Ph, and R² is Me. 619 Q¹ is 2-Br-6-F-Ph, and R² isCl. 620 Q¹ is 2-Br-6-F-Ph, and R² is Br. 621 Q¹ is 2-Me-4-F-Ph, and R²is Me. 622 Q¹ is 2-Me-4-F-Ph, and R² is Cl. 623 Q¹ is 2-Me-4-F-Ph, andR² is Br. 624 Q¹ is 2-I-4-F-Ph, and R² is Me. 625 Q¹ is 2-I-4-F-Ph, andR² is Cl. 626 Q¹ is 2-I-4-F-Ph, and R² is Br. 627 Q¹ is 2-F-Ph, and R²is Me. 628 Q¹ is 2-F-Ph, and R² is Cl. 629 Q¹ is 2-F-Ph, and R² is Br.630 Q¹ is 2-Cl-Ph, and R² is Me. 631 Q¹ is 2-Cl-Ph, and R² is Cl. 632 Q¹is 2-Cl-Ph, and R² is Br. 633 Q¹ is 2-Br-Ph, and R² is Me. 634 Q¹ is2-Br-Ph, and R² is Cl. 635 Q¹ is 2-Br-Ph, and R² is Br. 636 Q¹ is2-F-4-Cl-Ph, and R² is Me. 637 Q¹ is 2-F-4-Cl-Ph, and R² is Cl. 638 Q¹is 2-F-4-Cl-Ph, and R² is Br. 639 Q¹ is 2,4-di-Cl-Ph, and R² is Me. 640Q¹ is 2,4-di-Cl-Ph, and R² is Cl. 641 Q¹ is 2,4-di-Cl-Ph, and R² is Br.642 Q¹ is 2,6-di-Cl-Ph, and R² is Me. 643 Q¹ is 2,6-di-Cl-Ph, and R² isCl. 644 Q¹ is 2,6-di-Cl-Ph, and R² is Br. 645 Q¹ is 2-F-4-MeO-Ph, and R²is Me. 646 Q¹ is 2-F-4-MeO-Ph, and R² is Cl. 647 Q¹ is 2-F-4-MeO-Ph, andR² is Br. 647A Q¹ is 2-F-4-EtO-Ph, and R² is Me. 647B Q¹ is2-F-4-EtO-Ph, and R² is Cl. 647C Q¹ is 2-F-4-EtO-Ph, and R² is Br. 648Q¹ is 2-Cl-4-MeO-Ph, and R² is Me. 649 Q¹ is 2-Cl-4-MeO-Ph, and R² isCl. 650 Q¹ is 2-Cl-4-MeO-Ph, and R² is Br. 650A Q¹ is 2-Cl-4-EtO-Ph, andR² is Me. 650B Q¹ is 2-Cl-4-EtO-Ph, and R² is Cl. 650C Q¹ is2-Cl-4-EtO-Ph, and R² is Br. 651 Q¹ is 2-Br-4-MeO-Ph, and R² is Me. 652Q¹ is 2-Br-4-MeO-Ph, and R² is Cl. 653 Q¹ is 2-Br-4-MeO-Ph, and R² isBr. 653A Q¹ is 2-Br-4-EtO-Ph, and R² is Me. 653B Q¹ is 2-Br-4-EtO-Ph,and R² is Cl. 653C Q¹ is 2-Br-4-EtO-Ph, and R² is Br. 654 Q¹ is2-F-4-CN-Ph, and R² is Me. 655 Q¹ is 2-F-4-CN-Ph, and R² is Cl. 656 Q¹is 2-F-4-CN-Ph, and R² is Br. 657 Q¹ is 2-Cl-4-CN-Ph, and R² is Me. 658Q¹ is 2-Cl-4-CN-Ph, and R² is Cl. 659 Q¹ is 2-Cl-4-CN-Ph, and R² is Br.660 Q¹ is 2-Br-4-CN-Ph, and R² is Me. 661 Q¹ is 2-Br-4-CN-Ph, and R² isCl. 662 Q¹ is 2-Br-4-CN-Ph, and R² is Br. 663 Q¹ is2,5-di-Cl-3-pyridinyl, and R² is Me. 664 Q¹ is 2,5-di-Cl-3-pyridinyl,and R² is Cl. 665 Q¹ is 2,5-di-Cl-3-pyridinyl, and R² is Br. 666 Q¹ is2-Cl-3-thienyl, and R² is Me. 667 Q¹ is 2-Cl-3-thienyl, and R² is Cl.668 Q¹ is 2-Cl-3-thienyl, and R² is Br. 669 Q¹ is 2,5-di-Cl-3-thienyl,and R² is Me. 670 Q¹ is 2,5-di-Cl-3-thienyl, and R² is Cl. 671 Q¹ is2,5-di-Cl-3-thienyl, and R² is Br.

The compounds of Tables 588 through 671 illustrate compounds of Formula2 wherein X is NH, which are useful intermediates to prepare compoundsof Formula 1 using the method of Scheme 2.

TABLE 672

Q¹ Q¹ Q¹ Q¹ 2,6-di-F—Ph 2-Cl-4,6-di-F—Ph 2-Cl—Ph 2-Br-4-MeO—Ph2,4-di-F—Ph 4-Cl-2,6-di-F—Ph 2-Br—Ph 2-F-4-CN—Ph 2,4,6-tri-F—Ph2-Br-4-F—Ph 2-F-4-Cl—Ph 2-Cl-4-CN—Ph 2,6-di-F-4-OMe—Ph 2-Br-6-F—Ph2,4-di-Cl—Ph 2-Br-4-CN—Ph 2,6-di-F-4-CN—Ph 2-Me-4-F—Ph 2,6-di-Cl—Ph2,5-di-Cl-3-pyridinyl 2-Cl-4-F—Ph 2-I-4-F—Ph 2-F-4-MeO—Ph 2-Cl-3-thienyl2-Cl-6-F—Ph 2-F—Ph 2-Cl-4-MeO—Ph 2,5-di-Cl-3-thienyl 2,6-di-F-4-EtO—Ph2-F-4-EtO—Ph 2-Cl-4-EtO—Ph 2-Br-4-EtO—Ph G¹ is —OH.

The present disclosure also includes Tables 673 through 676, each ofwhich is constructed the same as Table 672 above, except that the rowheading in Table 672 (i.e. “G¹ is —OH.”) is replaced with the respectiverow heading shown below. For Example, in Table 673 the row heading is“G¹ is —SH.”, and Q¹ is as defined in Table 672 above. Thus, the firstentry in Table 673 specifically discloses4-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-thiol. Tables 674through 676 are constructed similarly.

Table Row Heading 673 G¹ is —SH. 674 G¹ is Cl. 675 G¹ is Br. 675A G¹ isI. 676 G¹ is —NH₂.

The compounds of Tables 672 and 673 illustrate compounds of Formula 4wherein X is O or S, R¹ and R^(1a) are each H, and R² is CH₃, which areuseful intermediates to prepare compounds of Formula 1 using the methodof Scheme 3. The compounds of Table 672 further illustrate compounds ofFormula 4b wherein R¹ and R^(1a) are each H, and R² is CH₃, which areuseful intermediates to prepare intermediate compounds of Formula 6ausing the method of Scheme 6 and to prepare intermediate compounds ofFormula 6b using the method of Scheme 7. Tables 674 and 675 illustratecompounds of Formula 6 wherein G is Cl or Br, and R^(1a) are each H, andR² is CH₃ which are useful intermediates to prepare compounds of Formula1c using the method of Scheme 4. Table 676 illustrates compounds ofFormula 4a wherein R¹ and R^(1a) are each H, and R² is CH₃, which areuseful intermediates to prepare intermediate compounds of Formula 6using the method of Scheme 5.

TABLE 677

(R³)_(p) (R³)_(p) (R³)_(p) (R³)_(p) (R³)_(p) 2-F 3-F 4-F 2-Cl 3-Cl 4-Cl2-Br 3-Br 4-Br 2,4-di-F 2,6-di-F 2,4,6-tri-F 2,4,5-tri-F 2,3,5-tri-F2,3,6-tri-F 2-Cl-4-F 2-F-4-Cl 2,4-di-Cl 2,6-di-Cl 2,4,6-tri-Cl 2-Br-4-F2-I-4-F 2-Me-4-F 2-F-4-MeO 2-Cl-4-MeO 2-Br-4-MeO 2,6-di-F-4-MeO 2-F-4-CN2-Cl-4-CN 2-Br-4-CN 2,6-di-F-4-CN 2-Cl-4,5-di-F 2-Cl-4,6-di-F2-Br-4,5-di-F 2-Br-4,6-di-F 4-Cl-2,5-di-F 4-Cl-2,6-di-F 4-Br-2,5-di-F4-Br-2,6-di-F 2,4-di-Cl-6-F 2,6-di-Cl-4-F 2,6-di-Cl-4-MeO 2-CF₃-4-F 4-Me2,4-di-Me 2-F-4-Br 2-Cl-4-Br 2-Br-4-Cl 2-Br-4-F-6-Cl 2-Cl-4-Br-6-F Q¹ is2,6-di-F—Ph, and R³² is Me.

The present disclosure also includes Tables 678 through 704, each ofwhich is constructed the same as Table 677 above, except that the rowheading in Table 677 (i.e. “Q¹ is 2,6-di-F-Ph.”) is replaced with therespective row heading shown below. For Example, in Table 2 the rowheading is “Q¹ is 2,4-di-F-Ph.”, and (R³)_(p) is as defined in Table 677above. Thus, the first entry in Table 678 specifically discloses3-(2,6-difluorophenyl)-4-[(2,4-difluorophenyl)amino]-4-(methylthio)-3-buten-2-one.Tables 679 through 704 are constructed similarly.

Table Row Heading 678 Q¹ is 2,4-di-F-Ph, and R³² is Me. 679 Q¹ is2,4,6-tri-F-Ph, and R³² is Me. 680 Q¹ is 2,6-di-F-4-OMe-Ph, and R³² isMe. 680A Q¹ is 2,6-di-F-4-OEt-Ph, and R³² is Me. 681 Q¹ is2,6-di-F-4-CN-Ph, and R³² is Me. 682 Q¹ is 2-Cl-4-F-Ph, and R³² is Me.683 Q¹ is 2-Cl-6-F-Ph, and R³² is Me. 684 Q¹ is 2-Cl-4,6-di-F-Ph, andR³² is Me. 685 Q¹ is 4-Cl-2,6-di-F-Ph, and R³² is Me. 686 Q¹ is2-Br-4-F-Ph, and R³² is Me. 687 Q¹ is 2-Br-6-F-Ph, and R³² is Me. 688 Q¹is 2-Me-4-F-Ph, and R³² is Me. 689 Q¹ is 2-I-4-F-Ph, and R³² is Me. 690Q¹ is 2-F-Ph, and R³² is Me. 691 Q¹ is 2-Cl-Ph, and R³² is Me. 692 Q¹ is2-Br-Ph, and R³² is Me. 693 Q¹ is 2-F-4-Cl-Ph, and R³² is Me. 694 Q¹ is2,4-di-Cl-Ph, and R³² is Me. 695 Q¹ is 2,6-di-Cl-Ph, and R³² is Me. 696Q¹ is 2-F-4-MeO-Ph, and R³² is Me. 696A Q¹ is 2-F-4-EtO-Ph, and R³² isMe. 697 Q¹ is 2-Cl-4-MeO-Ph, and R³² is Me. 697A Q¹ is 2-Cl-4-EtO-Ph,and R³² is Me. 698 Q¹ is 2-Br-4-MeO-Ph, and R³² is Me. 698A Q¹ is2-Br-4-EtO-Ph, and R³² is Me. 699 Q¹ is 2-F-4-CN-Ph, and R³² is Me. 700Q¹ is 2-Cl-4-CN-Ph, and R³² is Me. 701 Q¹ is 2-Br-4-CN-Ph, and R³² isMe. 702 Q¹ is 2,5-di-Cl-3-pyridinyl, and R³² is Me. 703 Q¹ is2-Cl-3-thienyl, and R³² is Me. 704 Q¹ is 2,5-di-Cl-3-thienyl, and R³² isMe. 705 Q¹ is 2,6-di-F-Ph, and R³² is Et. 706 Q¹ is 2,4-di-F-Ph, and R³²is Et. 707 Q¹ is 2,4,6-tri-F-Ph, and R³² is Et. 708 Q¹ is2,6-di-F-4-OMe-Ph, and R³² is Et. 708A Q¹ is 2,6-di-F-4-OEt-Ph, and R³²is Et. 709 Q¹ is 2,6-di-F-4-CN-Ph, and R³² is Et. 710 Q¹ is 2-Cl-4-F-Ph,and R³² is Et. 711 Q¹ is 2-Cl-6-F-Ph, and R³² is Et. 712 Q¹ is2-Cl-4,6-di-F-Ph, and R³² is Et. 713 Q¹ is 4-Cl-2,6-di-F-Ph, and R³² isEt. 714 Q¹ is 2-Br-4-F-Ph, and R³² is Et. 715 Q¹ is 2-Br-6-F-Ph, and R³²is Et. 716 Q¹ is 2-Me-4-F-Ph, and R³² is Et. 717 Q¹ is 2-I-4-F-Ph, andR³² is Et. 718 Q¹ is 2-F-Ph, and R³² is Et. 719 Q¹ is 2-Cl-Ph, and R³²is Et. 720 Q¹ is 2-Br-Ph, and R³² is Et. 721 Q¹ is 2-F-4-Cl-Ph, and R³²is Et. 722 Q¹ is 2,4-di-Cl-Ph, and R³² is Et. 723 Q¹ is 2,6-di-Cl-Ph,and R³² is Et. 724 Q¹ is 2-F-4-MeO-Ph, and R³² is Et. 724A Q¹ is2-F-4-EtO-Ph, and R³² is Et. 725 Q¹ is 2-Cl-4-MeO-Ph, and R³² is Et.725A Q¹ is 2-Cl-4-EtO-Ph, and R³² is Et. 726 Q¹ is 2-Br-4-MeO-Ph, andR³² is Et. 726A Q¹ is 2-Br-4-EtO-Ph, and R³² is Et. 727 Q¹ is2-F-4-CN-Ph, and R³² is Et. 728 Q¹ is 2-Cl-4-CN-Ph, and R³² is Et. 729Q¹ is 2-Br-4-CN-Ph, and R³² is Et. 730 Q¹ is 2,5-di-Cl-3-pyridinyl, andR³² is Et. 731 Q¹ is 2-Cl-3-thienyl, and R³² is Et. 732 Q¹ is2,5-di-Cl-3-thienyl, and R³² is Et. 733 Q¹ is 2,6-di-F-Ph, and R³² isn-Pr. 734 Q¹ is 2,4-di-F-Ph, and R³² is n-Pr. 735 Q¹ is 2,4,6-tri-F-Ph,and R³² is n-Pr. 736 Q¹ is 2,6-di-F-4-OMe-Ph, and R³² is n-Pr. 736A Q¹is 2,6-di-F-4-OEt-Ph, and R³² is n-Pr. 737 Q¹ is 2,6-di-F-4-CN-Ph, andR³² is n-Pr. 738 Q¹ is 2-Cl-4-F-Ph, and R³² is n-Pr. 739 Q¹ is2-Cl-6-F-Ph, and R³² is n-Pr. 740 Q¹ is 2-Cl-4,6-di-F-Ph, and R³² isn-Pr. 741 Q¹ is 4-Cl-2,6-di-F-Ph, and R³² is n-Pr. 742 Q¹ is2-Br-4-F-Ph, and R³² is n-Pr. 743 Q¹ is 2-Br-6-F-Ph, and R³² is n-Pr.744 Q¹ is 2-Me-4-F-Ph, and R³² is n-Pr. 745 Q¹ is 2-I-4-F-Ph, and R³² isn-Pr. 746 Q¹ is 2-F-Ph, and R³² is n-Pr. 747 Q¹ is 2-Cl-Ph, and R³² isn-Pr. 748 Q¹ is 2-Br-Ph, and R³² is n-Pr. 749 Q¹ is 2-F-4-Cl-Ph, and R³²is n-Pr. 750 Q¹ is 2,4-di-Cl-Ph, and R³² is n-Pr. 751 Q¹ is2,6-di-Cl-Ph, and R³² is n-Pr. 752 Q¹ is 2-F-4-MeO-Ph, and R³² is n-Pr.752A Q¹ is 2-F-4-EtO-Ph, and R³² is n-Pr. 753 Q¹ is 2-Cl-4-MeO-Ph, andR³² is n-Pr. 753A Q¹ is 2-Cl-4-EtO-Ph, and R³² is n-Pr. 754 Q¹ is2-Br-4-MeO-Ph, and R³² is n-Pr. 754A Q¹ is 2-Br-4-EtO-Ph, and R³² isn-Pr. 755 Q¹ is 2-F-4-CN-Ph, and R³² is n-Pr. 756 Q¹ is 2-Cl-4-CN-Ph,and R³² is n-Pr. 757 Q¹ is 2-Br-4-CN-Ph, and R³² is n-Pr. 758 Q¹ is2,5-di-Cl-3-pyridinyl, and R³² is n-Pr. 759 Q¹ is 2-Cl-3-thienyl, andR³² is n-Pr. 760 Q¹ is 2,5-di-Cl-3-thienyl, and R³² is n-Pr.

The compounds of Tables 677 through 760 illustrate compounds of Formula17 wherein R² is CH₃, which are useful intermediates to preparecompounds of Formula 1c using the method of Scheme 16.

TABLE 761

Q¹ Q¹ Q¹ Q¹ 2,6-di-F—Ph 2-Cl-4,6-di-F—Ph 2-Cl—Ph 2-Br-4-MeO—Ph2,4-di-F—Ph 4-Cl-2,6-di-F—Ph 2-Br—Ph 2-F-4-CN—Ph 2,4,6-tri-F—Ph2-Br-4-F—Ph 2-F-4-Cl—Ph 2-Cl-4-CN—Ph 2,6-di-F-4-OMe—Ph 2-Br-6-F—Ph2,4-di-Cl—Ph 2-Br-4-CN—Ph 2,6-di-F-4-CN—Ph 2-Me-4-F—Ph 2,6-di-Cl—Ph2,5-di-Cl-3-pyridinyl 2-Cl-4-F—Ph 2-I-4-F—Ph 2-F-4-MeO—Ph 2-Cl-3-thienyl2-Cl-6-F—Ph 2-F—Ph 2-Cl-4-MeO—Ph 2,5-di-Cl-3-thienyl 2,6-di-F-4-EtO—Ph2-F-4-EtO—Ph 2-Cl-4-EtO—Ph 2-Br-4-EtO—Ph Each R³³ is Me.

The present disclosure also includes Tables 762 through 764, each ofwhich is constructed the same as Table 761 above, except that the rowheading in Table 761 (i.e. “Each R³³ is Me.”) is replaced with therespective row heading shown below. For Example, in Table 762 the rowheading is “Each R³³ is Et.”, and Q¹ is as defined in Table 761 above.Thus, the first entry in Table 762 specifically discloses3-(2,6-difluorophenyl)-4,4-bis(ethylthio)-3-buten-2-one. Tables 763 and764 are constructed similarly.

Table Row Heading 762 Each R³³ is Et. 763 Each R³³ is n-Pr. 764 The twoR³³ are taken together as —CH₂—.

The compounds of Tables 761 through 763 illustrate compounds of Formula18 wherein R² is CH₃, which are useful intermediates to prepareintermediate compounds of Formula 17 using the method of Scheme 17. Thecompounds of Table 764 illustrate compounds of Formula 18 wherein R² isCH₃, which are useful intermediates to prepare intermediate compounds ofFormula 4c using the method described below Scheme 17.

TABLE 765

Q¹ Q¹ Q¹ Q¹ 2,6-di-F—Ph 2-Cl-4,6-di-F—Ph 2-Cl—Ph 2-Br-4-MeO—Ph2,4-di-F—Ph 4-Cl-2,6-di-F—Ph 2-Br—Ph 2-F-4-CN—Ph 2,4,6-tri-F—Ph2-Br-4-F—Ph 2-F-4-Cl—Ph 2-Cl-4-CN—Ph 2,6-di-F-4-OMe—Ph 2-Br-6-F—Ph2,4-di-Cl—Ph 2-Br-4-CN—Ph 2,6-di-F-4-CN—Ph 2-Me-4-F—Ph 2,6-di-Cl—Ph2,5-di-Cl-3-pyridinyl 2-Cl-4-F—Ph 2-I-4-F—Ph 2-F-4-MeO—Ph 2-Cl-3-thienyl2-Cl-6-F—Ph 2-F—Ph 2-Cl-4-MeO—Ph 2,5-di-Cl-3-thienyl 2,6-di-F-4-EtO—Ph2-F-4-EtO—Ph 2-Cl-4-EtO—Ph 2-Br-4-EtO—Ph B¹ is Me.

The present disclosure also includes Tables 766 through 769, each ofwhich is constructed the same as Table 765 above, except that the rowheading in Table 765 (i.e. “B¹ is Me.”) is replaced with the respectiverow heading shown below. For Example, in Table 766 the row heading is“B¹ is Et.”, and Q¹ is as defined in Table 765 above. Thus, the firstentry in Table 766 specifically discloses ethylα-acetyl-2,6-difluorobenzeneacetate. Tables 767 through 769 areconstructed similarly

Table Row Heading 766 B¹ is Et. 767 B¹ is is n-Pr. 768 B¹ is Ph. 769 B¹is CH₂Ph.

The compounds of Tables 765 through 769 illustrate compounds of Formula16 wherein R² is CH₃, which are useful intermediates to prepareintermediate compounds of Formula 4b using the method of Scheme 14.

Formulation/Utility

A compound of this invention will generally be used as a fungicidalactive ingredient in a composition, i.e. formulation, with at least oneadditional component selected from the group consisting of surfactants,solid diluents and liquid diluents, which serves as a carrier. Theformulation or composition ingredients are selected to be consistentwith the physical properties of the active ingredient, mode ofapplication and environmental factors such as soil type, moisture andtemperature.

Useful formulations include both liquid and solid compositions. Liquidcompositions include solutions (including emulsifiable concentrates),suspensions, emulsions (including microemulsions and/or suspoemulsions)and the like, which optionally can be thickened into gels. The generaltypes of aqueous liquid compositions are soluble concentrate, suspensionconcentrate, capsule suspension, concentrated emulsion, microemulsionand suspo-emulsion. The general types of nonaqueous liquid compositionsare emulsifiable concentrate, microemulsifiable concentrate, dispersibleconcentrate and oil dispersion.

The general types of solid compositions are dusts, powders, granules,pellets, prills, pastilles, tablets, filled films (including seedcoatings) and the like, which can be water-dispersible (“wettable”) orwater-soluble. Films and coatings formed from film-forming solutions orflowable suspensions are particularly useful for seed treatment. Activeingredient can be (micro)encapsulated and further formed into asuspension or solid formulation; alternatively the entire formulation ofactive ingredient can be encapsulated (or “overcoated”). Encapsulationcan control or delay release of the active ingredient. An emulsifiablegranule combines the advantages of both an emulsifiable concentrateformulation and a dry granular formulation. High-strength compositionsare primarily used as intermediates for further formulation.

Sprayable formulations are typically extended in a suitable mediumbefore spraying. Such liquid and solid formulations are formulated to bereadily diluted in the spray medium, usually water. Spray volumes canrange from about from about one to several thousand liters per hectare,but more typically are in the range from about ten to several hundredliters per hectare. Sprayable formulations can be tank mixed with wateror another suitable medium for foliar treatment by aerial or groundapplication, or for application to the growing medium of the plant.Liquid and dry formulations can be metered directly into drip irrigationsystems or metered into the furrow during planting. Liquid and solidformulations can be applied onto seeds of crops and other desirablevegetation as seed treatments before planting to protect developingroots and other subterranean plant parts and/or foliage through systemicuptake.

The formulations will typically contain effective amounts of activeingredient, diluent and surfactant within the following approximateranges which add up to 100 percent by weight.

Weight Percent Active Ingredient Diluent Surfactant Water-Dispersibleand Water- 0.001-90 0-99.999  0-15 soluble Granules, Tablets and PowdersOil Dispersions, Suspensions,    1-50 40-99     0-50 Emulsions,Solutions (including Emulsifiable Concentrates) Dusts    1-25 70-99   0-5 Granules and Pellets 0.001-95 5-99.999  0-15 High StrengthCompositions   90-99 0-10    0-2

Solid diluents include, for example, clays such as bentonite,montmorillonite, attapulgite and kaolin, gypsum, cellulose, titaniumdioxide, zinc oxide, starch, dextrin, sugars (e.g., lactose, sucrose),silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodiumcarbonate and bicarbonate, and sodium sulfate. Typical solid diluentsare described in Watkins et al., Handbook of Insecticide Dust Diluentsand Carriers, 2nd Ed., Dorland Books, Caldwell, N.J.

Liquid diluents include, for example, water, N,N-dimethylalkanamides(e.g., N,N-dimethylformamide), limonene, dimethyl sulfoxide,N-alkylpyrrolidones (e.g., N-methylpyrrolidinone), ethylene glycol,triethylene glycol, propylene glycol, dipropylene glycol, polypropyleneglycol, propylene carbonate, butylene carbonate, paraffins (e.g., whitemineral oils, normal paraffins, isoparaffins), alkylbenzenes,alkylnaphthalenes, glycerine, glycerol triacetate, sorbitol, triacetin,aromatic hydrocarbons, dearomatized aliphatics, alkylbenzenes,alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone,isophorone and 4-hydroxy-4-methyl-2-pentanone, acetates such as isoamylacetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate,tridecyl acetate and isobornyl acetate, other esters such as alkylatedlactate esters, dibasic esters and γ-butyrolactone, and alcohols, whichcan be linear, branched, saturated or unsaturated, such as methanol,ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol,n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecyl alcohol,isooctadecanol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oleylalcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol andbenzyl alcohol. Liquid diluents also include glycerol esters ofsaturated and unsaturated fatty acids (typically C₆-C₂₂), such as plantseed and fruit oils (e.g, oils of olive, castor, linseed, sesame, corn(maize), peanut, sunflower, grapeseed, safflower, cottonseed, soybean,rapeseed, coconut and palm kernel), animal-sourced fats (e.g., beeftallow, pork tallow, lard, cod liver oil, fish oil), and mixturesthereof. Liquid diluents also include alkylated fatty acids (e.g.,methylated, ethylated, butylated) wherein the fatty acids may beobtained by hydrolysis of glycerol esters from plant and animal sources,and can be purified by distillation. Typical liquid diluents aredescribed in Marsden, Solvents Guide, 2nd Ed., Interscience, New York,1950.

The solid and liquid compositions of the present invention often includeone or more surfactants. When added to a liquid, surfactants (also knownas “surface-active agents”) generally modify, most often reduce, thesurface tension of the liquid. Depending on the nature of thehydrophilic and lipophilic groups in a surfactant molecule, surfactantscan be useful as wetting agents, dispersants, emulsifiers or defoamingagents.

Surfactants can be classified as nonionic, anionic or cationic. Nonionicsurfactants useful for the present compositions include, but are notlimited to: alcohol alkoxylates such as alcohol alkoxylates based onnatural and synthetic alcohols (which may be branched or linear) andprepared from the alcohols and ethylene oxide, propylene oxide, butyleneoxide or mixtures thereof; amine ethoxylates, alkanolamides andethoxylated alkanolamides; alkoxylated triglycerides such as ethoxylatedsoybean, castor and rapeseed oils; alkylphenol alkoxylates such asoctylphenol ethoxylates, nonylphenol ethoxylates, dinonyl phenolethoxylates and dodecyl phenol ethoxylates (prepared from the phenolsand ethylene oxide, propylene oxide, butylene oxide or mixturesthereof); block polymers prepared from ethylene oxide or propylene oxideand reverse block polymers where the terminal blocks are prepared frompropylene oxide; ethoxylated fatty acids; ethoxylated fatty esters andoils; ethoxylated methyl esters; ethoxylated tristyrylphenol (includingthose prepared from ethylene oxide, propylene oxide, butylene oxide ormixtures thereof); fatty acid esters, glycerol esters, lanolin-basedderivatives, polyethoxylate esters such as polyethoxylated sorbitanfatty acid esters, polyethoxylated sorbitol fatty acid esters andpolyethoxylated glycerol fatty acid esters; other sorbitan derivativessuch as sorbitan esters; polymeric surfactants such as randomcopolymers, block copolymers, alkyd peg (polyethylene glycol) resins,graft or comb polymers and star polymers; polyethylene glycols (pegs);polyethylene glycol fatty acid esters; silicone-based surfactants; andsugar-derivatives such as sucrose esters, alkyl polyglycosides and alkylpolysaccharides.

Useful anionic surfactants include, but are not limited to: alkylarylsulfonic acids and their salts; carboxylated alcohol or alkylphenolethoxylates; diphenyl sulfonate derivatives; lignin and ligninderivatives such as lignosulfonates; maleic or succinic acids or theiranhydrides; olefin sulfonates; phosphate esters such as phosphate estersof alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates andphosphate esters of styryl phenol ethoxylates; protein-basedsurfactants; sarcosine derivatives; styryl phenol ether sulfate;sulfates and sulfonates of oils and fatty acids; sulfates and sulfonatesof ethoxylated alkylphenols; sulfates of alcohols; sulfates ofethoxylated alcohols; sulfonates of amines and amides such asN,N-alkyltaurates; sulfonates of benzene, cumene, toluene, xylene, anddodecyl and tridecylbenzenes; sulfonates of condensed naphthalenes;sulfonates of naphthalene and alkyl naphthalene; sulfonates offractionated petroleum; sulfosuccinamates; and sulfosuccinates and theirderivatives such as dialkyl sulfosuccinate salts.

Useful cationic surfactants include, but are not limited to: amides andethoxylated amides; amines such as N-alkyl propanediamines,tripropylenetriamines and dipropylenetetramines, and ethoxylated amines,ethoxylated diamines and propoxylated amines (prepared from the aminesand ethylene oxide, propylene oxide, butylene oxide or mixturesthereof); amine salts such as amine acetates and diamine salts;quaternary ammonium salts such as quaternary salts, ethoxylatedquaternary salts and diquaternary salts; and amine oxides such asalkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.

Also useful for the present compositions are mixtures of nonionic andanionic surfactants or mixtures of nonionic and cationic surfactants.Nonionic, anionic and cationic surfactants and their recommended usesare disclosed in a variety of published references includingMcCutcheon's Emulsifiers and Detergents, annual American andInternational Editions published by McCutcheon's Division, TheManufacturing Confectioner Publishing Co.; Sisely and Wood, Encyclopediaof Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; andA. S. Davidson and B. Milwidsky, Synthetic Detergents, Seventh Edition,John Wiley and Sons, New York, 1987.

Compositions of this invention may also contain formulation auxiliariesand additives, known to those skilled in the art as formulation aids(some of which may be considered to also function as solid diluents,liquid diluents or surfactants). Such formulation auxiliaries andadditives may control: pH (buffers), foaming during processing(antifoams such polyorganosiloxanes), sedimentation of activeingredients (suspending agents), viscosity (thixotropic thickeners),in-container microbial growth (antimicrobials), product freezing(antifreezes), color (dyes/pigment dispersions), wash-off (film formersor stickers), evaporation (evaporation retardants), and otherformulation attributes. Film formers include, for example, polyvinylacetates, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinylacetate copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers andwaxes. Examples of formulation auxiliaries and additives include thoselisted in McCutcheon's Volume 2: Functional Materials, annualInternational and North American editions published by McCutcheon'sDivision, The Manufacturing Confectioner Publishing Co.; and PCTPublication WO 03/024222.

The compound of Formula 1 and any other active ingredients are typicallyincorporated into the present compositions by dissolving the activeingredient in a solvent or by grinding in a liquid or dry diluent.Solutions, including emulsifiable concentrates, can be prepared bysimply mixing the ingredients. If the solvent of a liquid compositionintended for use as an emulsifiable concentrate is water-immiscible, anemulsifier is typically added to emulsify the active-containing solventupon dilution with water. Active ingredient slurries, with particlediameters of up to 2,000 μm can be wet milled using media mills toobtain particles with average diameters below 3 μm. Aqueous slurries canbe made into finished suspension concentrates (see, for example, U.S.Pat. No. 3,060,084) or further processed by spray drying to formwater-dispersible granules. Dry formulations usually require dry millingprocesses, which produce average particle diameters in the 2 to 10 mrange. Dusts and powders can be prepared by blending and usuallygrinding (such as with a hammer mill or fluid-energy mill). Granules andpellets can be prepared by spraying the active material upon preformedgranular carriers or by agglomeration techniques. See Browning,“Agglomeration”, Chemical Engineering, Dec. 4, 1967, pp 147-48, Perry'sChemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963,pages 8-57 and following, and WO 91/13546. Pellets can be prepared asdescribed in U.S. Pat. No. 4,172,714.

Water-dispersible and water-soluble granules can be prepared as taughtin U.S. Pat. No. 4,144,050, U.S. Pat. No. 3,920,442 and DE 3,246,493.Tablets can be prepared as taught in U.S. Pat. No. 5,180,587, U.S. Pat.No. 5,232,701 and U.S. Pat. No. 5,208,030. Films can be prepared astaught in GB 2,095,558 and U.S. Pat. No. 3,299,566.

For further information regarding the art of formulation, see T. S.Woods, “The Formulator's Toolbox—Product Forms for Modern Agriculture”in Pesticide Chemistry and Bioscience, The Food-Environment Challenge,T. Brooks and T. R. Roberts, Eds., Proceedings of the 9th InternationalCongress on Pesticide Chemistry, The Royal Society of Chemistry,Cambridge, 1999, pp. 120-133. See also U.S. Pat. No. 3,235,361, Col. 6,line 16 through Col. 7, line 19 and Examples 10-41; U.S. Pat. No.3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12,15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182;U.S. Pat. No. 2,891,855, Col. 3, line 66 through Col. 5, line 17 andExamples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons,Inc., New York, 1961, pp 81-96; Hance et al., Weed Control Handbook, 8thEd., Blackwell Scientific Publications, Oxford, 1989; and Developmentsin formulation technology, PJB Publications, Richmond, U K, 2000.

In the following Examples, all percentages are by weight and allformulations are prepared in conventional ways. Compound numbers referto compounds in Index Table A. Without further elaboration, it isbelieved that one skilled in the art using the preceding description canutilize the present invention to its fullest extent. The followingExamples are, therefore, to be construed as merely illustrative, and notlimiting of the disclosure in any way whatsoever. Percentages are byweight except where otherwise indicated.

Example A

High Strength Concentrate Compound 18 98.5% silica aerogel  0.5%synthetic amorphous fine silica  1.0%

Example B

Wettable Powder Compound 22 65.0% dodecylphenol polyethylene glycolether  2.0% sodium ligninsulfonate  4.0% sodium silicoaluminate  6.0%montmorillonite (calcined) 23.0%

Example C

Granule Compound 23 10.0% attapulgite granules (low volatile matter,90.0% 0.71/0.30 mm; U.S.S. No. 25-50 sieves)

Example D

Extruded Pellet Compound 24 25.0% anhydrous sodium sulfate 10.0% crudecalcium ligninsulfonate  5.0% sodium alkylnaphthalenesulfonate  1.0%calcium/magnesium bentonite 59.0%

Example E

Emulsifiable Concentrate Compound 36 10.0% polyoxyethylene sorbitolhexoleate 20.0% C₆—C₁₀ fatty acid methyl ester 70.0%

Example F

Microemulsion Compound 41  5.0% polyvinylpyrrolidone-vinyl acetatecopolymer 30.0% alkylpolyglycoside 30.0% glyceryl monooleate 15.0% water20.0%

Example G

Seed Treatment Compound 45 20.00% polyvinylpyrrolidone-vinyl acetatecopolymer  5.00% montan acid wax  5.00% calcium ligninsulfonate  1.00%polyoxyethylene/polyoxypropylene block copolymers  1.00% stearyl alcohol(POE 20)  2.00% polyorganosilane  0.20% colorant red dye  0.05% water65.75%

Formulations such as those in the Formulation Table are typicallydiluted with water to form aqueous compositions before application.Aqueous compositions for direct applications to the plant or portionthereof (e.g., spray tank compositions) typically at least about 1 ppmor more (e.g., from 1 ppm to 100 ppm) of the compound(s) of thisinvention.

The compounds of this invention are useful as plant disease controlagents. The present invention therefore further comprises a method forcontrolling plant diseases caused by fungal plant pathogens comprisingapplying to the plant or portion thereof to be protected, or to theplant seed to be protected, an effective amount of a compound of theinvention or a fungicidal composition containing said compound. Thecompounds and/or compositions of this invention provide control ofdiseases caused by a broad spectrum of fungal plant pathogens in theBasidiomycete, Ascomycete, Oomycete and Deuteromycete classes. They areeffective in controlling a broad spectrum of plant diseases,particularly foliar pathogens of ornamental, turf, vegetable, field,cereal, and fruit crops. These pathogens include: Oomycetes, includingPhytophthora diseases such as Phytophthora infestans, Phytophthoramegasperma, Phytophthora parasitica, Phytophthora cinnamomi andPhytophthora capsici, Pythium diseases such as Pythium aphanidermatum,and diseases in the Peronosporaceae family such as Plasmopara viticola,Peronospora spp. (including Peronospora tabacina and Peronosporaparasitica), Pseudoperonospora spp. (including Pseudoperonosporacubensis) and Bremia lactucae; Ascomycetes, including Alternariadiseases such as Alternaria solani and Alternaria brassicae, Guignardiadiseases such as Guignardia bidwell, Venturia diseases such as Venturiainaequalis, Septoria diseases such as Septoria nodorum and Septoriatritici, powdery mildew diseases such as Erysiphe spp. (includingErysiphe graminis and Erysiphe polygoni), Uncinula necatur, Sphaerothecafuligena and Podosphaera leucotricha, Pseudocercosporellaherpotrichoides, Botrytis diseases such as Botrytis cinerea, Moniliniafructicola, Sclerotinia diseases such as Sclerotinia sclerotiorum,Magnaporthe grisea, Phomopsis viticola, Helminthosporium diseases suchas Helminthosporium tritici repentis, Pyrenophora teres, anthracnosediseases such as Glomerella or Colletotrichum spp. (such asColletotrichum graminicola and Colletotrichum orbiculare), andGaeumannomyces graminis; Basidiomycetes, including rust diseases causedby Puccinia spp. (such as Puccinia recondita, Puccinia striiformis,Puccinia hordei, Puccinia graminis and Puccinia arachidis), Hemileiavastatrix and Phakopsora pachyrhizi; other pathogens includingRutstroemia floccosum (also known as Sclerontina homoeocarpa);Rhizoctonia spp. (such as Rhizoctonia solani); Fusarium diseases such asFusarium roseum, Fusarium gramninearum and Fusarium oxysporum;Verticillium dahliae; Sclerotium rolfsii; Rynchosporium secalis;Cercosporidium personatum, Cercospora arachidicola and Cercosporabeticola; and other genera and species closely related to thesepathogens. In addition to their fungicidal activity, the compositions orcombinations also have activity against bacteria such as Erwiniaamylovora, Xanthomonas campestris, Pseudomonas syringae, and otherrelated species.

Plant disease control is ordinarily accomplished by applying aneffective amount of a compound of this invention either pre- orpost-infection, to the portion of the plant to be protected such as theroots, stems, foliage, fruit, seeds, tubers or bulbs, or to the media(soil or sand) in which the plants to be protected are growing. Thecompounds can also be applied to seeds to protect the seeds andseedlings developing from the seeds. The compounds can also be appliedthrough irrigation water to treat plants.

Accordingly, this aspect of the present invention can also be describedas a method for protecting a plant or plant seed from diseases caused byfungal pathogens comprising applying a fungicidally effective amount ofa compound of Formula 1, an N-oxide, or salt thereof to the plant (orportion thereof) or plant seed (directly or through the environment(e.g., growing medium) of the plant or plant seed).

Rates of application for these compounds can be influenced by manyfactors of the environment and should be determined under actual useconditions. Foliage can normally be protected when treated at a rate offrom less than about 1 g/ha to about 5,000 g/ha of active ingredient.Seed and seedlings can normally be protected when seed is treated at arate of from about 0.1 to about 10 g per kilogram of seed.

Compounds of this invention can also be mixed with one or more otherbiologically active compounds or agents including fungicides,insecticides, nematocides, bactericides, acaricides, herbicides,herbicide safeners, growth regulators such as insect molting inhibitorsand rooting stimulants, chemosterilants, semiochemicals, repellents,attractants, pheromones, feeding stimulants, plant nutrients, otherbiologically active compounds or entomopathogenic bacteria, virus orfungi to form a multi-component pesticide giving an even broaderspectrum of agricultural protection. Thus the present invention alsopertains to a composition comprising a fungicidally effective amount ofa compound of Formula 1 and a biologically effective amount of at leastone additional biologically active compound or agent and can furthercomprise at least one of a surfactant, a solid diluent or a liquiddiluent. The other biologically active compounds or agents can beformulated in compositions comprising at least one of a surfactant,solid or liquid diluent. For mixtures of the present invention, one ormore other biologically active compounds or agents can be formulatedtogether with a compound of Formula 1, to form a premix, or one or moreother biologically active compounds or agents can be formulatedseparately from the compound of Formula 1, and the formulations combinedtogether before application (e.g., in a spray tank) or, alternatively,applied in succession.

As mentioned in the Summary of the Invention, one aspect of the presentinvention is a fungicidal composition comprising (i.e. a mixture orcombination of) a compound of Formula 1, an N-oxide, or a salt thereof(i.e. component a), and at least one other fungicide (i.e. component b).

Of note is a composition which, in addition to the Formula 1 compound ofcomponent (a), includes as component (b) at least one fungicidalcompound selected from the group consisting of the classes (b1) methylbenzimidazole carbamate (MBC) fungicides; (b2) dicarboximide fungicides;(b3) demethylation inhibitor (DMI) fungicides; (b4) phenylamidefungicides; (b5) amine/morpholine fungicides; (b6) phospholipidbiosynthesis inhibitor fungicides; (b7) carboxamide fungicides; (b8)hydroxy(2-amino-)pyrimidine fungicides; (b9) anilinopyrimidinefungicides; (b10) N-phenyl carbamate fungicides; (b11) quinone outsideinhibitor (QoI) fungicides; (b12) phenylpyrrole fungicides; (b13)quinoline fungicides; (b14) lipid peroxidation inhibitor fungicides;(b15) melanin biosynthesis inhibitors-reductase (MBI-R) fungicides;(b16) melanin biosynthesis inhibitors-dehydratase (MBI-D) fungicides;(b17) hydroxyanilide fungicides; (b18) squalene-epoxidase inhibitorfungicides; (b19) polyoxin fungicides; (b20) phenylurea fungicides;(b21) quinone inside inhibitor (QiI) fungicides; (b22) benzamidefungicides; (b23) enopyranuronic acid antibiotic fungicides; (b24)hexopyranosyl antibiotic fungicides; (b25) glucopyranosyl antibiotic:protein synthesis fungicides; (b26) glucopyranosyl antibiotic: trehalaseand inositol biosynthesis fungicides; (b27) cyanoacetamideoximefungicides; (b28) carbamate fungicides; (b29) oxidative phosphorylationuncoupling fungicides; (b30) organo tin fungicides; (b31) carboxylicacid fungicides; (b32) heteroaromatic fungicides; (b33) phosphonatefungicides; (b34) phthalamic acid fungicides; (b35) benzotriazinefungicides; (b36) benzene-sulfonamide fungicides; (b37) pyridazinonefungicides; (b38) thiophene-carboxamide fungicides; (b39) pyrimidinamidefungicides; (b40) carboxylic acid amide (CAA) fungicides; (b41)tetracycline antibiotic fungicides; (b42) thiocarbamate fungicides;(b43) benzamide fungicides; (b44) host plant defense inductionfungicides; (b45) multi-site contact activity fungicides; (b46)fungicides other than classes (b1) through (b45); and salts of compoundsof classes (b1) through (b46).

Further descriptions of these classes of fungicidal compounds areprovided below.

(b1) “Methyl benzimidazole carbamate (MBC) fungicides” (FRAC (FungicideResistance Action Committee) code 1) inhibit mitosis by binding toβ-tubulin during microtubule assembly. Inhibition of microtubuleassembly can disrupt cell division, transport within the cell and cellstructure. Methyl benzimidazole carbamate fungicides includebenzimidazole and thiophanate fungicides. The benzimidazoles includebenomyl, carbendazim, fuberidazole and thiabendazole. The thiophanatesinclude thiophanate and thiophanate-methyl.

(b2) “Dicarboximide fungicides” (FRAC code 2) are proposed to inhibit alipid peroxidation in fungi through interference with NADH cytochrome creductase. Examples include chlozolinate, iprodione, procymidone andvinclozolin.

(b3) “Demethylation inhibitor (DMI) fungicides” (FRAC code 3) inhibitC14-demethylase which plays a role in sterol production. Sterols, suchas ergosterol, are needed for membrane structure and function, makingthem essential for the development of functional cell walls. Therefore,exposure to these fungicides result in abnormal growth and eventuallydeath of sensitive fungi. DMI fungicides are divided between severalchemical classes: azoles (including triazoles and imidazoles),pyrimidines, piperazines and pyridines. The triazoles includeazaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole,diniconazole (including diniconazole-M), epoxiconazole, etaconazole,fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole,imibenconazole, ipconazole, metconazole, myclobutanil, penconazole,propiconazole, prothioconazole, quinconazole, simeconazole,tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole anduniconazole. The imidazoles include clotrimazole, econazole, imazalil,isoconazole, miconazole, oxpoconazole, prochloraz, pefurazoate andtriflumizole. The pyrimidines include fenarimol, nuarimol and triarimol.The piperazines include triforine. The pyridines include buthiobate andpyrifenox. Biochemical investigations have shown that all of the abovementioned fungicides are DMI fungicides as described by K. H. Kuck etal. in Modern Selective Fungicides—Properties, Applications andMechanisms of Action, H. Lyr (Ed.), Gustav Fischer Verlag: New York,1995, 205-258.

(b4) “Phenylamide fungicides” (FRAC code 4) are specific inhibitors ofRNA polymerase in Oomycete fungi. Sensitive fungi exposed to thesefungicides show a reduced capacity to incorporate uridine into rRNA.Growth and development in sensitive fungi is prevented by exposure tothis class of fungicide. Phenylamide fungicides include acylalanine,oxazolidinone and butyrolactone fungicides. The acylalanines includebenalaxyl, benalaxyl-M, furalaxyl, metalaxyl, metalaxyl-M (also known asmefenoxam). The oxazolidinones include oxadixyl. The butyrolactonesinclude ofurace.

(b5) “Amine/morpholine fungicides” (FRAC code 5) inhibit two targetsites within the sterol biosynthetic pathway, Δ⁸→Δ⁷ isomerase and Δ¹⁴reductase. Sterols, such as ergosterol, are needed for membranestructure and function, making them essential for the development offunctional cell walls. Therefore, exposure to these fungicides resultsin abnormal growth and eventually death of sensitive fungi.Amine/morpholine fungicides (also known as non-DMI sterol biosynthesisinhibitors) include morpholine, piperidine and spiroketal-aminefungicides. The morpholines include aldimorph, dodemorph, fenpropimorph,tridemorph and trimorphamide. The piperidines include fenpropidin andpiperalin. The spiroketal-amines include spiroxamine.

(b6) “Phospholipid biosynthesis inhibitor fungicides” (FRAC code 6)inhibit growth of fungi by affecting phospholipid biosynthesis.Phospholipid biosynthesis fungicides include phosphorothiolate anddithiolane fungicides. The phosphorothiolates include edifenphos,iprobenfos and pyrazophos. The dithiolanes include isoprothiolane.

(b7) “Carboxamide fungicides” (FRAC code 7) inhibit Complex II(succinate dehydrogenase) fungal respiration by disrupting a key enzymein the Krebs Cycle (TCA cycle) named succinate dehydrogenase. Inhibitingrespiration prevents the fungus from making ATP, and thus inhibitsgrowth and reproduction. Carboxamide fungicides include benzamide, furancarboxamide, oxathiin carboxamide, thiazole carboxamide, pyrazolecarboxamide and pyridine carboxamide. The benzamides include benodanil,flutolanil and mepronil. The furan carboxamides include fenfuram. Theoxathiin carboxamides include carboxin and oxycarboxin. The thiazolecarboxamides include thifluzamide. The pyrazole carboxamides includebixafen, furametpyr, isopyrazam, fluxapyroxad, sedaxane(N-[2-(1S,2R)-[1,1′-bicyclopropyl]-2-ylphenyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide)and penflufen(N-[2-(1,3-dimethylbutyl)phenyl]-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide(PCT Patent Publication WO 2003/010149)). The pyridine carboxamidesinclude boscalid.

(b8) “Hydroxy(2-amino-)pyrimidine fungicides” (FRAC code 8) inhibitnucleic acid synthesis by interfering with adenosine deaminase. Examplesinclude bupirimate, dimethirimol and ethirimol.

(b9) “Anilinopyrimidine fungicides” (FRAC code 9) are proposed toinhibit biosynthesis of the amino acid methionine and to disrupt thesecretion of hydrolytic enzymes that lyse plant cells during infection.Examples include cyprodinil, mepanipyrim and pyrimethanil.

(b10) “N-Phenyl carbamate fungicides” (FRAC code 10) inhibit mitosis bybinding to β-tubulin and disrupting microtubule assembly. Inhibition ofmicrotubule assembly can disrupt cell division, transport within thecell and cell structure. Examples include diethofencarb.

(b11) “Quinone outside inhibitor (QoI) fungicides” (FRAC code 11)inhibit Complex III mitochondrial respiration in fungi by affectingubiquinol oxidase. Oxidation of ubiquinol is blocked at the “quinoneoutside” (Q_(o)) site of the cytochrome bc₁ complex, which is located inthe inner mitochondrial membrane of fungi. Inhibiting mitochondrialrespiration prevents normal fungal growth and development. Quinoneoutside inhibitor fungicides (also known as strobilurin fungicides)include methoxyacrylate, methoxycarbamate, oximinoacetate,oximinoacetamide, oxazolidinedione, dihydrodioxazine, imidazolinone andbenzylcarbamate fungicides. The methoxyacrylates include azoxystrobin,enestroburin (SYP-Z071) and picoxystrobin. The methoxycarbamates includepyraclostrobin and pyrametostrobin. The oximinoacetates includekresoxim-methyl, pyraoxystrobin and trifloxystrobin. Theoximinoacetamides include dimoxystrobin, metominostrobin, orysastrobin,α-[methoxyimino]-N-methyl-2-[[[1-[3-(trifluoromethyl)phenyl]ethoxy]imino]-methyl]benzeneacetamideand2-[[[3-(2,6-dichlorophenyl)-1-methyl-2-propen-1-ylidene]-amino]oxy]methyl]-α-(methoxyimino)-N-methylbenzeneacetamide.The oxazolidinediones include famoxadone. The dihydrodioxazines includefluoxastrobin. The imidazolinones include fenamidone. Thebenzylcarbamates include pyribencarb.

(b12) “Phenylpyrrole fungicides” (FRAC code 12) inhibit a MAP proteinkinase associated with osmotic signal transduction in fungi. Fenpicloniland fludioxonil are examples of this fungicide class.

(b13) “Quinoline fungicides” (FRAC code 13) are proposed to inhibitsignal transduction by affecting G-proteins in early cell signaling.They have been shown to interfere with germination and/or appressoriumformation in fungi that cause powder mildew diseases. Quinoxyfen is anexample of this class of fungicide.

(b14) “Lipid peroxidation inhibitor fungicides” (FRAC code 14) areproposed to inhibit lipid peroxidation which affects membrane synthesisin fungi. Members of this class, such as etridiazole, may also affectother biological processes such as respiration and melanin biosynthesis.Lipid peroxidation fungicides include aromatic carbon and1,2,4-thiadiazole fungicides. The aromatic carbon fungicides includebiphenyl, chloroneb, dicloran, quintozene, tecnazene andtolclofos-methyl. The 1,2,4-thiadiazole fungicides include etridiazole.

(b15) “Melanin biosynthesis inhibitors-reductase (MBI-R) fungicides”(FRAC code 16.1) inhibit the naphthal reduction step in melaninbiosynthesis. Melanin is required for host plant infection by somefungi. Melanin biosynthesis inhibitors-reductase fungicides includeisobenzofuranone, pyrroloquinolinone and triazolobenzothiazolefungicides. The isobenzofuranones include fthalide. Thepyrroloquinolinones include pyroquilon. The triazolobenzothiazolesinclude tricyclazole.

(b16) “Melanin biosynthesis inhibitors-dehydratase (MBI-D) fungicides”(FRAC code 16.2) inhibit scytalone dehydratase in melanin biosynthesis.Melanin in required for host plant infection by some fungi. Melaninbiosynthesis inhibitors-dehydratase fungicides includecyclopropanecarboxamide, carboxamide and propionamide fungicides. Thecyclopropanecarboxamides include carpropamid. The carboxamides includediclocymet. The propionamides include fenoxanil.

(b17) “Hydroxyanilide fungicides (FRAC code 17) inhibit C4-demethylasewhich plays a role in sterol production. Examples include fenhexamid.

(b18) “Squalene-epoxidase inhibitor fungicides” (FRAC code 18) inhibitsqualene-epoxidase in ergosterol biosynthesis pathway. Sterols such asergosterol are needed for membrane structure and function, making themessential for the development of functional cell walls. Thereforeexposure to these fungicides results in abnormal growth and eventuallydeath of sensitive fungi. Squalene-epoxidase inhibitor fungicidesinclude thiocarbamate and allylamine fungicides. The thiocarbamatesinclude pyributicarb. The allylamines include naftifine and terbinafine.

(b19) “Polyoxin fungicides” (FRAC code 19) inhibit chitin synthase.Examples include polyoxin.

(b20) “Phenylurea fungicides” (FRAC code 20) are proposed to affect celldivision. Examples include pencycuron.

(b21) “Quinone inside inhibitor (QiI) fungicides” (FRAC code 21) inhibitComplex III mitochondrial respiration in fungi by affecting ubiquinolreductase. Reduction of ubiquinol is blocked at the “quinone inside”(Q_(i)) site of the cytochrome bc₁ complex, which is located in theinner mitochondrial membrane of fungi. Inhibiting mitochondrialrespiration prevents normal fungal growth and development. Quinoneinside inhibitor fungicides include cyanoimidazole and sulfamoyltriazolefungicides. The cyanoimidazoles include cyazofamid. Thesulfamoyltriazoles include amisulbrom.

(b22) “Benzamide fungicides” (FRAC code 22) inhibit mitosis by bindingto β-tubulin and disrupting microtubule assembly. Inhibition ofmicrotubule assembly can disrupt cell division, transport within thecell and cell structure. Examples include zoxamide.

(b23) “Enopyranuronic acid antibiotic fungicides” (FRAC code 23) inhibitgrowth of fungi by affecting protein biosynthesis. Examples includeblasticidin-S.

(b24) “Hexopyranosyl antibiotic fungicides” (FRAC code 24) inhibitgrowth of fungi by affecting protein biosynthesis. Examples includekasugamycin.

(b25) “Glucopyranosyl antibiotic: protein synthesis fungicides” (FRACcode 25) inhibit growth of fungi by affecting protein biosynthesis.Examples include streptomycin.

(b26) “Glucopyranosyl antibiotic: trehalase and inositol biosynthesisfungicides” (FRAC code 26) inhibit trehalase in inositol biosynthesispathway. Examples include validamycin.

(b27) “Cyanoacetamideoxime fungicides (FRAC code 27) include cymoxanil.

(b28) “Carbamate fungicides” (FRAC code 28) are considered multi-siteinhibitors of fungal growth. They are proposed to interfere with thesynthesis of fatty acids in cell membranes, which then disrupts cellmembrane permeability. Propamacarb, propamacarb-hydrochloride, iodocarb,and prothiocarb are examples of this fungicide class.

(b29) “Oxidative phosphorylation uncoupling fungicides” (FRAC code 29)inhibit fungal respiration by uncoupling oxidative phosphorylation.Inhibiting respiration prevents normal fungal growth and development.This class includes 2,6-dinitroanilines such as fluazinam,pyrimidonehydrazones such as ferimzone and dinitrophenyl crotonates suchas dinocap, meptyldinocap and binapacryl.

(b30) “Organo tin fungicides” (FRAC code 30) inhibit adenosinetriphosphate (ATP) synthase in oxidative phosphorylation pathway.Examples include fentin acetate, fentin chloride and fentin hydroxide.

(b31) “Carboxylic acid fungicides” (FRAC code 31) inhibit growth offungi by affecting deoxyribonucleic acid (DNA) topoisomerase type II(gyrase). Examples include oxolinic acid.

(b32) “Heteroaromatic fungicides” (FRAC code 32) are proposed to affectDNA/ribonucleic acid (RNA) synthesis. Heteroaromatic fungicides includeisoxazole and isothiazolone fungicides. The isoxazoles includehymexazole and the isothiazolones include octhilinone.

(b33) “Phosphonate fungicides” (FRAC code 33) include phosphorous acidand its various salts, including fosetyl-aluminum.

(b34) “Phthalamic acid fungicides” (FRAC code 34) include teclofthalam.

(b35) “Benzotriazine fungicides” (FRAC code 35) include triazoxide.

(b36) “Benzene-sulfonamide fungicides” (FRAC code 36) includeflusulfamide.

(b37) “Pyridazinone fungicides” (Fungicide Resistance Action Committee(FRAC) code 37) include diclomezine.

(b38) “Thiophene-carboxamide fungicides” (FRAC code 38) are proposed toaffect ATP production. Examples include silthiofam.

(b39) “Pyrimidinamide fungicides” (FRAC code 39) inhibit growth of fungiby affecting phospholipid biosynthesis and include diflumetorim.

(b40) “Carboxylic acid amide (CAA) fungicides” (FRAC code 40) areproposed to inhibit phospholipid biosynthesis and cell wall deposition.Inhibition of these processes prevents growth and leads to death of thetarget fungus. Carboxylic acid amide fungicides include cinnamic acidamide, valinamide carbamate and mandelic acid amide fungicides. Thecinnamic acid amides include dimethomorph and flumorph. The valinamidecarbamates include benthiavalicarb, benthiavalicarb-isopropyl,iprovalicarb and valifenalate (valiphenal). The mandelic acid amidesinclude mandipropamid,N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(methylsulfonyl)-amino]butanamideandN-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]-ethyl]-3-methyl-2-[(ethylsulfonyl)amino]butanamide.

(b41) “Tetracycline antibiotic fungicides” (FRAC code 41) inhibit growthof fungi by affecting complex 1 nicotinamide adenine dinucleotide (NADH)oxidoreductase. Examples include oxytetracycline.

(b42) “Thiocarbamate fungicides (b42)” (FRAC code 42) includemethasulfocarb.

(b43) “Benzamide fungicides” (FRAC code 43) inhibit growth of fungi bydelocalization of spectrin-like proteins. Examples include acylpicolidefungicides such as fluopicolide and fluopyram.

(b44) “Host plant defense induction fungicides” (FRAC code P) inducehost plant defense mechanisms. Host plant defense induction fungicidesinclude benzo-thiadiazole, benzisothiazole and thiadiazole-carboxamidefungicides. The benzo-thiadiazoles include acibenzolar-S-methyl. Thebenzisothiazoles include probenazole. The thiadiazole-carboxamidesinclude tiadinil and isotianil.

(b45) “Multi-site contact fungicides” inhibit fungal growth throughmultiple sites of action and have contact/preventive activity. Thisclass of fungicides includes: (b45.1) “copper fungicides” (FRAC codeM1)”, (b45.2) “sulfur fungicides” (FRAC code M2), (b45.3)“dithiocarbamate fungicides” (FRAC code M3), (b45.4) “phthalimidefungicides” (FRAC code M4), (b45.5) “chloronitrile fungicides” (FRACcode M5), (b45.6) “sulfamide fungicides” (FRAC code M6), (b45.7)“guanidine fungicides” (FRAC code M7), (b45.8) “triazine fungicides”(FRAC code M8) and (b45.9) “quinone fungicides” (FRAC code M9). “Copperfungicides” are inorganic compounds containing copper, typically in thecopper(II) oxidation state; examples include copper oxychloride, coppersulfate and copper hydroxide, including compositions such as Bordeauxmixture (tribasic copper sulfate). “Sulfur fungicides” are inorganicchemicals containing rings or chains of sulfur atoms; examples includeelemental sulfur. “Dithiocarbamate fungicides” contain a dithiocarbamatemolecular moiety; examples include mancozeb, metiram, propineb, ferbam,maneb, thiram, zineb and ziram. “Phthalimide fungicides” contain aphthalimide molecular moiety; examples include folpet, captan andcaptafol. “Chloronitrile fungicides” contain an aromatic ringsubstituted with chloro and cyano; examples include chlorothalonil.“Sulfamide fungicides” include dichlofluanid and tolyfluanid. “Guanidinefungicides” include dodine, guazatine and imoctadine, includingiminoctadine albesilate and iminoctadine triacetate. “Triazinefungicides” include anilazine. “Quinone fungicides” include dithianon.

(b46) “Fungicides other than fungicides of classes (b1) through (b45)”include certain fungicides whose mode of action may be unknown. Theseinclude: (b46.1) “thiazole carboxamide fungicides” (FRAC code US),(b46.2) “phenyl-acetamide fungicides” (FRAC code U6), (b46.3)“quinazolinone fungicides” (FRAC code U7) and (b46.4) “benzophenonefungicides” (FRAC code U8). The thiazole carboxamides include ethaboxam.The phenyl-acetamides include cyflufenamid andN-[[(cyclopropylmethoxy)amino][6-(difluoromethoxy)-2,3-difluorophenyl]-methylene]benzeneacetamide.The quinazolinones include proquinazid and2-butoxy-6-iodo-3-propyl-4H-1-benzopyran-4-one. The benzophenonesinclude metrafenone and pyriofenone. The (b46) class also includesbethoxazin, neo-asozin (ferric methanearsonate), fenpyrazamine,pyrrolnitrin, quinomethionate, tebufloquin,N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(methylsulfonyl)amino]butanamide,N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(ethylsulfonyl)amino]-butanamide,2-[[2-fluoro-5-(trifluoromethyl)phenyl]thio]-2-[3-(2-methoxyphenyl)-2-thiazolidinylidene]acetonitrile,3-[5-(4-chlorophenyl)-2,3-dimethyl-3-isoxazolidinyl]pyridine,4-fluorophenylN-[1-[[[1-(4-cyanophenyl)ethyl]sulfonyl]methyl]propyl]carbamate,5-chloro-6-(2,4,6-trifluorophenyl)-7-(4-methylpiperidin-1-yl)[1,2,4]triazolo[1,5-a]pyrimidine,N-(4-chloro-2-nitrophenyl)-N-ethyl-4-methylbenzenesulfonamide,N-[[(cyclopropylmethoxy)-amino][6-(difluoromethoxy)-2,3-difluorophenyl]methylene]benzeneacetamide,N-[4-[4-chloro-3-(trifluoromethyl)phenoxy]-2,5-dimethylphenyl]-N-ethyl-N-methylmethanimidamideand1-[(2-propenylthio)carbonyl]-2-(1-methylethyl)-4-(2-methylphenyl)-5-amino-1H-pyrazol-3-one.

Therefore of note is a mixture (i.e. composition) comprising ascomponent (a) a compound of Formula 1 (or an N-oxide or salt thereof)and as component (b) at least one fungicidal compound selected from thegroup consisting of the aforedescribed classes (b1) through (b46). Alsoof note are embodiments wherein component (b) comprises at least onefungicide from each of two different groups selected from (b1) through(b46). Also of note is a composition comprising said mixture (infungicidally effective amount) and further comprising at least oneadditional component selected from the group consisting of surfactants,solid diluents and liquid diluents. Of particular note is a mixture(i.e. composition) comprising a compound of Formula 1 and at least onefungicidal compound selected from the group of specific compounds listedabove in connection with classes (b1) through (b46). Also of particularnote is a composition comprising said mixture (in fungicidally effectiveamount) and further comprising at least one additional surfactantselected from the group consisting of surfactants, solid diluents andliquid diluents.

Examples of other biologically active compounds or agents with whichcompounds of this invention can be formulated are: insecticides such asabamectin, acephate, acetamiprid, acetoprole, aldicarb, amidoflumet(S-1955), amitraz, avermectin, azadirachtin, azinphos-methyl,bifenthrin, bifenazate, bistrifluron, buprofezin, carbofuran, cartap,chinomethionat, chlorfenapyr, chlorfluazuron, chlorantraniliprole(DPX-E2Y45), chlorpyrifos, chlorpyrifos-methyl, chlorobenzilate,chromafenozide, clothianidin, cyantraniliprole(3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-[(methylamino)-carbonyl]phenyl]-1H-pyrazole-5-carboxamide),cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin,gamma-cyhalothrin, lambda-cyhalothrin, cyhexatin, cypermethrin,cyromazine, deltamethrin, diafenthiuron, diazinon, dicofol, dieldrin,dienochlor, diflubenzuron, dimefluthrin, dimethoate, dinotefuran,diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, etoxazole,fenamiphos, fenazaquin, fenbutatin oxide, fenothiocarb, fenoxycarb,fenpropathrin, fenpyroximate, fenvalerate, fipronil, flonicamid,flubendiamide, flucythrinate, tau-fluvalinate, flufenerim (UR-50701),flufenoxuron, fonophos, halofenozide, hexaflumuron, hexythiazox,hydramethylnon, imicyafos, imidacloprid, indoxacarb, isofenphos,lufenuron, malathion, metaflumizone, metaldehyde, methamidophos,methidathion, methomyl, methoprene, methoxychlor, methoxyfenozide,metofluthrin, monocrotophos, nitenpyram, nithiazine, novaluron(XDE-007), noviflumuron, oxamyl, parathion, parathion-methyl,permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb,profenofos, profluthrin, propargite, prothiocarb, protrifenbute,pymetrozine, pyrafluprole, pyrethrin, pyridaben, pyridalyl,pyrifluquinazon, pyriprole, pyriproxyfen, rotenone, ryanodine,spinetoram, spinosad, spiridiclofen, spiromesifen (BSN 2060),spirotetramat, sulprofos, tebufenozide, tebufenpyrad, teflubenzuron,tefluthrin, terbufos, tetrachlorvinphos, thiacloprid, thiamethoxam,thiodicarb, thiosultap-sodium, tolfenpyrad, tralomethrin, triazamate,trichlorfon, triflumuron; nematocides such as aldicarb, imicyafos,oxamyl and fenamiphos; bactericides such as streptomycin; acaricidessuch as amitraz, chinomethionat, chlorobenzilate, cyenopyrafen,cyhexatin, dicofol, dienochlor, etoxazole, fenazaquin, fenbutatin oxide,fenpropathrin, fenpyroximate, hexythiazox, propargite, pyridaben andtebufenpyrad; and biological agents including entomopathogenic bacteria,such as Bacillus thuringiensis subsp. aizawai, Bacillus thuringiensissubsp. kurstaki, and the encapsulated delta-endotoxins of Bacillusthuringiensis (e.g., Cellcap, MPV, MPVII); entomopathogenic fungi, suchas green muscardine fungus; and entomopathogenic virus includingbaculovirus, nucleopolyhedro virus (NPV) such as HzNPV, AfNPV; andgranulosis virus (GV) such as CpGV.

General references for agricultural protectants (i.e. insecticides,fungicides, nematocides, acaricides, herbicides and biological agents)include The Pesticide Manual, 13th Edition, C. D. S. Tomlin, Ed.,British Crop Protection Council, Farnham, Surrey, U. K., 2003 and TheBioPesticide Manual, 2nd Edition, L. G. Copping, Ed., British CropProtection Council, Farnham, Surrey, U. K., 2001.

For embodiments where one or more of these various mixing partners areused, the weight ratio of these various mixing partners (in total) tothe compound of Formula 1 (or an N-oxide or salt thereof) is typicallybetween about 1:3000 and about 3000:1. Of note are weight ratios betweenabout 1:300 and about 300:1 (for example ratios between about 1:30 andabout 30:1). One skilled in the art can easily determine through simpleexperimentation the biologically effective amounts of active ingredientsnecessary for the desired spectrum of biological activity. It will beevident that including these additional components may expand thespectrum of diseases controlled beyond the spectrum controlled by thecompound of Formula 1 alone.

In certain instances, combinations of a compound of this invention withother biologically active (particularly fungicidal) compounds or agents(i.e. active ingredients) can result in a greater-than-additive (i.e.synergistic) effect. Reducing the quantity of active ingredientsreleased in the environment while ensuring effective pest control isalways desirable. When synergism of fungicidal active ingredients occursat application rates giving agronomically satisfactory levels of fungalcontrol, such combinations can be advantageous for reducing cropproduction cost and decreasing environmental load.

Compounds of this invention and compositions thereof can be applied toplants genetically transformed to express proteins toxic to invertebratepests (such as Bacillus thuringiensis delta-endotoxins). The effect ofthe exogenously applied fungicidal compounds of this invention may besynergistic with the expressed toxin proteins.

Of note is a combination of a compound of Formula 1 (or an N-oxide orsalt thereof) with at least one other fungicidal active ingredient. Ofparticular note is such a combination where the other fungicidal activeingredient has different site of action from the compound of Formula 1.In certain instances, a combination with at least one other fungicidalactive ingredient having a similar spectrum of control but a differentsite of action will be particularly advantageous for resistancemanagement. Thus, a composition of the present invention can furthercomprise a biologically effective amount of at least one additionalfungicidal active ingredient having a similar spectrum of control but adifferent site of action.

Of particular note are compositions which in addition to a compound ofFormula 1 include at least one compound selected from the groupconsisting of (1) alkylenebis(dithiocarbamate) fungicides; (2)cymoxanil; (3) phenylamide fungicides; (4) pyrimidinone fungicides; (5)chlorothalonil; (6) carboxamides acting at complex II of the fungalmitochondrial respiratory electron transfer site; (7) quinoxyfen; (8)metrafenone or pyriofenone; (9) cyflufenamid; (10) cyprodinil; (11)copper compounds; (12) phthalimide fungicides; (13) fosetyl-aluminum;(14) benzimidazole fungicides; (15) cyazofamid; (16) fluazinam; (17)iprovalicarb; (18) propamocarb; (19) validomycin; (20) dichlorophenyldicarboximide fungicides; (21) zoxamide; (22) fluopicolide; (23)mandipropamid; (24) carboxylic acid amides acting on phospholipidbiosynthesis and cell wall deposition; (25) dimethomorph; (26) non-DMIsterol biosynthesis inhibitors; (27) inhibitors of demethylase in sterolbiosynthesis; (28) bc₁ complex fungicides; and salts of compounds of (1)through (28).

Further descriptions of classes of fungicidal compounds are providedbelow.

Pyrimidinone fungicides (group (4)) include compounds of Formula A1

wherein M forms a fused phenyl, thiophene or pyridine ring; R^(a14) isC₁-C₆ alkyl; R^(a15) is C₁-C₆ alkyl or C₁-C₆ alkoxy; R^(a16) is halogen;and R^(a17) is hydrogen or halogen.

Pyrimidinone fungicides are described in PCT Patent ApplicationPublication WO 94/26722 and U.S. Pat. Nos. 6,066,638, 6,245,770,6,262,058 and 6,277,858. Of note are pyrimidinone fungicides selectedfrom the group: 6-bromo-3-propyl-2-propyloxy-4(3H)-quinazolinone,6,8-diiodo-3-propyl-2-propyloxy-4(3H)-quinazolinone,6-iodo-3-propyl-2-propyloxy-4(3H)-quinazolinone (proquinazid),6-chloro-2-propoxy-3-propylthieno[2,3-d]pyrimidin-4(3H)-one,6-bromo-2-propoxy-3-propylthieno[2,3-d]pyrimidin-4(3H)-one,7-bromo-2-propoxy-3-propylthieno[3,2-d]pyrimidin-4(3H)-one,6-bromo-2-propoxy-3-propylpyrido[2,3-d]pyrimidin-4(3H)-one,6,7-dibromo-2-propoxy-3-propylthieno[3,2-d]pyrimidin-4(3H)-one, and3-(cyclopropylmethyl)-6-iodo-2-(propylthio)pyrido-[2,3-d]pyrimidin-4(3H)-one.

Sterol biosynthesis inhibitors (group (27)) control fungi by inhibitingenzymes in the sterol biosynthesis pathway. Demethylase-inhibitingfungicides have a common site of action within the fungal sterolbiosynthesis pathway, involving inhibition of demethylation at position14 of lanosterol or 24-methylene dihydrolanosterol, which are precursorsto sterols in fungi. Compounds acting at this site are often referred toas demethylase inhibitors, DMI fungicides, or DMIs. The demethylaseenzyme is sometimes referred to by other names in the biochemicalliterature, including cytochrome P-450 (14DM). The demethylase enzyme isdescribed in, for example, J. Biol. Chem. 1992, 267, 13175-79 andreferences cited therein. DMI fungicides are divided between severalchemical classes: azoles (including triazoles and imidazoles),pyrimidines, piperazines and pyridines. The triazoles includeazaconazole, bromuconazole, cyproconazole, difenoconazole, diniconazole(including diniconazole-M), epoxiconazole, etaconazole, fenbuconazole,fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole,ipconazole, metconazole, myclobutanil, penconazole, propiconazole,prothioconazole, quinconazole, simeconazole, tebuconazole,tetraconazole, triadimefon, triadimenol, triticonazole and uniconazole.The imidazoles include clotrimazole, econazole, imazalil, isoconazole,miconazole, oxpoconazole, prochloraz and triflumizole. The pyrimidinesinclude fenarimol, nuarimol and triarimol. The piperazines includetriforine. The pyridines include buthiobate and pyrifenox. Biochemicalinvestigations have shown that all of the above mentioned fungicides areDMI fungicides as described by K. H. Kuck et al. in Modern SelectiveFungicides—Properties, Applications and Mechanisms of Action, H. Lyr(Ed.), Gustav Fischer Verlag: New York, 1995, 205-258.

bc₁ Complex Fungicides (group 28) have a fungicidal mode of action whichinhibits the bc₁ complex in the mitochondrial respiration chain. The bc₁complex is sometimes referred to by other names in the biochemicalliterature, including complex III of the electron transfer chain, andubihydroquinone:cytochrome c oxidoreductase. This complex is uniquelyidentified by Enzyme Commission number EC1.10.2.2. The bc₁ complex isdescribed in, for example, J. Biol. Chem. 1989, 264, 14543-48; MethodsEnzymol. 1986, 126, 253-71; and references cited therein. Strobilurinfungicides such as azoxystrobin, dimoxystrobin, enestroburin (SYP-Z071),fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin,picoxystrobin, pyraclostrobin and trifloxystrobin are known to have thismode of action (H. Sauter et al., Angew. Chem. Int. Ed. 1999, 38,1328-1349). Other fungicidal compounds that inhibit the bc₁ complex inthe mitochondrial respiration chain include famoxadone and fenamidone.

Alkylenebis(dithiocarbamate)s (group (1)) include compounds such asmancozeb, maneb, propineb and zineb. Phenylamides (group (3)) includecompounds such as metalaxyl, benalaxyl, furalaxyl and oxadixyl.Carboxamides (group (6)) include compounds such as boscalid, carboxin,fenfuram, flutolanil, fluxapyroxad, furametpyr, mepronil, oxycarboxin,thifluzamide, penthiopyrad and penflufen(N-[2-(1,3-dimethylbutyl)phenyl]-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide(PCT Patent Publication WO 2003/010149)), and are known to inhibitmitochondrial function by disrupting complex II (succinatedehydrogenase) in the respiratory electron transport chain. Coppercompounds (group (11)) include compounds such as copper oxychloride,copper sulfate and copper hydroxide, including compositions such asBordeaux mixture (tribasic copper sulfate). Phthalimides (group (12))include compounds such as folpet and captan. Benzimidazole fungicides(group (14)) include benomyl and carbendazim. Dichlorophenyldicarboximide fungicides (group (20)) include chlozolinate,dichlozoline, iprodione, isovaledione, myclozolin, procymidone andvinclozolin.

Non-DMI sterol biosynthesis inhibitors (group (26)) include morpholineand piperidine fungicides. The morpholines and piperidines are sterolbiosynthesis inhibitors that have been shown to inhibit steps in thesterol biosynthesis pathway at a point later than the inhibitionsachieved by the DMI sterol biosynthesis (group (27)). The morpholinesinclude aldimorph, dodemorph, fenpropimorph, tridemorph andtrimorphamide. The piperidines include fenpropidin.

Examples of component (b) fungicides include acibenzolar-S-methyl,aldimorph, ametoctradin, amisulbrom, anilazine, azaconazole,azoxystrobin, benalaxyl, benalaxyl-M, benodanil, benomyl,benthiavalicarb, benthiavalicarb-isopropyl, bethoxazin, binapacryl,biphenyl, bitertanol, bixafen, blasticidin-S, boscalid, bromuconazole,bupirimate, carboxin, carpropamid, captafol, captan, carbendazim,chloroneb, chlorothalonil, chlozolinate, clotrimazole, copper salts suchas Bordeaux mixture (tribasic copper sulfate), copper hydroxide andcopper oxychloride, cyazofamid, cyflufenamid, cymoxanil, cyproconazole,cyprodinil, dichlofluanid, diclocymet, diclomezine, dicloran,diethofencarb, difenoconazole, diflumetorim, dimethirimol, dimethomorph,dimoxystrobin, diniconazole, diniconazole-M, dinocap, dithianon,dodemorph, dodine, edifenphos, enestroburin, epoxiconazole, ethaboxam,ethirimol, etridiazole, famoxadone, fenamidone, fenarimol,fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil,fenpropidin, fenpropimorph, fenpyrazamine, fentin acetate, fentinchloride, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil,flumetover, flumorph, fluopicolide (also known as picobenzamid),fluopyram, fluoroimide, fluoxastrobin, fluquinconazole, flusilazole,flusulfamide, flutianil(2-[[2-fluoro-5-(trifluoromethyl)phenyl]thio]-2-[3-(2-methoxyphenyl)-2-thiazolidinylidene]acetonitrile),flutolanil, flutriafol, fluxapyroxad, folpet, fosetyl-aluminum,fuberidazole, furalaxyl, furametpyr, hexaconazole, hymexazol, guazatine,imazalil, imibenconazole, iminoctadine, iodocarb, ipconazole,iprobenfos, iprodione, iprovalicarb, isoprothiolane, isopyrazam,isotianil, kasugamycin, kresoxim-methyl, mancozeb, mandipropamid, maneb,mepronil, meptyldinocap, metalaxyl, metalaxyl-M, metconazole,methasulfocarb, metiram, metominostrobin, mepanipyrim, metrafenone,myclobutanil, naftifine, neo-asozin (ferric methanearsonate), nuarimol,octhilinone, ofurace, orysastrobin, oxadixyl, oxolinic acid,oxpoconazole, oxycarboxin, oxytetracycline, penconazole, pencycuron,penflufen, penthiopyrad, pefurazoate, phosphorous acid and salts,phthalide, picoxystrobin, piperalin, polyoxin, probenazole, prochloraz,procymidone, propamocarb, propamocarb-hydrochloride, propiconazole,propineb, proquinazid, prothioconazole, pyraclostrobin, pyrametostrobin,pyraoxystrobin, pyrazophos, pyribencarb, pyributicarb, pyrifenox,pyrimethanil, pyriofenone, pyroquilon, pyrrolnitrin, quinomethionate,quinoxyfen, quintozene, sedaxane, silthiofam, simeconazole, spiroxamine,streptomycin, sulfur, tebuconazole, tebufloquin, tecloftalam, tecnazene,terbinafine, tetraconazole, thiabendazole, thifluzamide, thiophanate,thiophanate-methyl, thiram, tiadinil, tolclofos-methyl, tolylfluanid,triadimefon, triadimenol, triazoxide, tricyclazole, tridemorph,triflumizole, tricyclazole, trifloxystrobin, triforine, trimorphamide,triticonazole, uniconazole, validamycin, valifenalate (valiphenal),vinclozolin, zineb, ziram, zoxamide,N′-[4-[4-chloro-3-(trifluoromethyl)phenoxy]-2,5-dimethylphenyl]-N-ethyl-N-methylmethanimidamide,5-chloro-6-(2,4,6-trifluorophenyl)-7-(4-methylpiperidin-1-yl)[1,2,4]triazolo[1,5-a]pyrimidine(BAS600), penflufen(N-[2-(1,3-dimethylbutyl)phenyl]-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide),N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(methylsulfonyl)amino]butanamide,N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(ethylsulfonyl)amino]butanamide,2-butoxy-6-iodo-3-propyl-4H-1-benzopyran-4-one,3-[5-(4-chlorophenyl)-2,3-dimethyl-3-isoxazolidinyl]-pyridine,4-fluorophenylN-[1-[[[1-(4-cyanophenyl)ethyl]sulfonyl]methyl]propyl]carbamate,N-[[(cyclopropylmethoxy)amino][6-(difluoromethoxy)-2,3-difluorophenyl]methylene]benzeneacetamide,α-(methoxyimino)-N-methyl-2-[[[1-[3-(trifluoro-methyl)phenyl]ethoxy]imino]methyl]benzeneacetamide,N-[4-[4-chloro-3-(trifluoro-methyl)phenoxy]-2,5-dimethylphenyl]-N-ethyl-N-methylmethanimidamide,N-(4-chloro-2-nitrophenyl)-N-ethyl-4-methylbenzenesulfonamide,2-[[[[3-(2,6-dichlorophenyl)-1-methyl-2-propen-1-ylidene]amino]oxy]methyl]-α-(methoxyimino)-N-methylbenzeneacetamide,1-[(2-propenylthio)carbonyl]-2-(1-methylethyl)-4-(2-methylphenyl)-5-amino-1H-pyrazol-3-one,ethyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine, pentylN-[4-[[[[(1-methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxy]methyl]-2-thiazolyl]carbamateand pentylN-[6-[[[[(1-methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxy]methyl]-2-pyridinyl]carbamate

Of note are combinations of compounds of Formula 1 (or an N-oxide orsalt thereof) (i.e. Component (a) in compositions) with azoxystrobin,kresoxim-methyl, trifloxystrobin, pyraclostrobin, picoxystrobin,pyrametostrobin, pyraoxystrobin, dimoxystrobin,metominostrobin/fenominostrobin, carbendazim, chlorothalonil,quinoxyfen, metrafenone, cyflufenamid, fenpropidine, fenpropimorph,bromuconazole, cyproconazole, difenoconazole, epoxiconazole,fenbuconazole, flusilazole, fluxapyroxad, hexaconazole, ipconazole,metconazole, penconazole, propiconazole, proquinazid, prothioconazole,pyriofenone, tebuconazole, triticonazole, famoxadone, prochloraz,penthiopyrad and boscalid (nicobifen) (i.e. as Component (b) incompositions).

Preferred for better control of plant diseases caused by fungal plantpathogens (e.g., lower use rate or broader spectrum of plant pathogenscontrolled) or resistance management are mixtures of a compound of thisinvention with a fungicide selected from the group: azoxystrobin,kresoxim-methyl, trifloxystrobin, pyraclostrobin, picoxystrobin,pyrametostrobin, pyraoxystrobin, dimoxystrobin,metominostrobin/fenominostrobin, quinoxyfen, metrafenone, cyflufenamid,fenpropidine, fenpropimorph, cyproconazole, epoxiconazole, flusilazole,metconazole, propiconazole, proquinazid, prothioconazole, pyriofenone,tebuconazole, triticonazole, famoxadone and penthiopyrad.

Tables A1 through A54 list specific combinations of a Component (b)compound with Component (a) (compound numbers refer to compounds inIndex Table A) illustrative of the mixtures, compositions and methods ofthe present invention. In Table A1, each line below the column headings“Component (a)” and “Component (b)” specifically discloses a combination(i.e. mixture) of Component (a), which is Compound 22, with a Component(b) fungicide. The entries under the heading “Illustrative Ratios”disclose three specific weight ratios of Component (b) to Component (a)for the disclosed mixture. For example, the first line of Table A1discloses a mixture of Compound 22 with acibenzolar-S-methyl and listsweight ratios of acibenzolar-S-methyl to Compound 22 of 1:1, 1:4 or1:17.

TABLE A1 Component (a) Component (b) Illustrative Ratios(*) Compound 22acibenzolar-S-methyl 1:1 1:4  1:18 Compound 22 aldimorph 7:1 3:1 1:1Compound 22 ametoctradin 3:1 1:1 1:3 Compound 22 amisulbrom 1:1 1:2 1:6Compound 22 anilazine 22:1  8:1 4:1 Compound 22 azaconazole 2:1 1:2 1:4Compound 22 azoxystrobin 3:1 1:1 1:3 Compound 22 benalaxyl 1:1 1:2 1:6Compound 22 benalaxyl-M 1:1 1:3 1:8 Compound 22 benodanil 4:1 2:1 1:2Compound 22 benomyl 11:1  4:1 1:1 Compound 22 benthiavalicarb 1:1 1:4 1:12 Compound 22 benthiavalicarb-isopropyl 1:1 1:4  1:12 Compound 22bethoxazin 15:1  5:1 2:1 Compound 22 binapacryl 15:1  5:1 2:1 Compound22 biphenyl 15:1  5:1 2:1 Compound 22 bitertanol 3:1 1:1 1:2 Compound 22bixafen 2:1 1:1 1:3 Compound 22 blasticidin-S 1:4  1:12  1:30 Compound22 Bordeaux mixture (tribasic copper sulfate) 45:1  15:1  5:1 Compound22 boscalid 4:1 2:1 1:2 Compound 22 bromuconazole 3:1 1:1 1:3 Compound22 bupirimate 1:3  1:10  1:30 Compound 22 captafol 15:1  5:1 2:1Compound 22 captan 15:1  5:1 2:1 Compound 22 carbendazim 11:1  4:1 2:1Compound 22 carboxin 4:1 2:1 1:2 Compound 22 carpropamid 3:1 1:1 1:3Compound 22 chloroneb 100:1  35:1  14:1  Compound 22 chlorothalonil 15:15:1 2:1 Compound 22 chlozolinate 11:1 4:1 2:1 Compound 22 clotrimazole3:1 1:1 1:3 Compound 22 copper hydroxide 45:1  15:1 5:1 Compound 22copper oxychloride 45:1  15:1 5:1 Compound 22 cyazofamid 1:1 1:2 1:6Compound 22 cyflufenamid 1:2 1:6  1:24 Compound 22 cymoxanil 1:1 1:2 1:5Compound 22 cyproconazole 1:1 1:2 1:6 Compound 22 cyprodinil 4:1 2:1 1:2Compound 22 dichlofluanid 15:1  5:1 2:1 Compound 22 diclocymet 15:1  5:12:1 Compound 22 diclomezine 3:1 1:1 1:3 Compound 22 dicloran 15:1  5:12:1 Compound 22 diethofencarb 7:1 2:1 1:2 Compound 22 difenoconazole 1:11:3  1:12 Compound 22 diflumetorim 15:1  5:1 2:1 Compound 22dimethirimol 1:3 1:8  1:30 Compound 22 dimethomorph 3:1 1:1 1:2 Compound22 dimoxystrobin 2:1 1:1 1:4 Compound 22 diniconazole 1:1 1:3 1:8Compound 22 diniconazole-M 1:1 1:3  1:12 Compound 22 dinocap 2:1 1:1 1:3Compound 22 dithianon 5:1 2:1 1:2 Compound 22 dodemorph 7:1 3:1 1:1Compound 22 dodine 10:1  4:1 2:1 Compound 22 edifenphos 3:1 1:1 1:3Compound 22 enestroburin 2:1 1:1 1:4 Compound 22 epoxiconazole 1:1 1:31:7 Compound 22 ethaboxam 2:1 1:1 1:3 Compound 22 ethirimol 7:1 3:1 1:1Compound 22 etridiazole 7:1 2:1 1:2 Compound 22 famoxadone 2:1 1:1 1:4Compound 22 fenamidone 2:1 1:1 1:4 Compound 22 fenarimol 1:2 1:7  1:24Compound 22 fenbuconazole 1:1 1:3  1:10 Compound 22 fenfuram 4:1 1:1 1:2Compound 22 fenhexamid 10:1  4:1 2:1 Compound 22 fenoxanil 15:1  4:1 1:1Compound 22 fenpiclonil 15:1  5:1 2:1 Compound 22 fenpropidin 7:1 2:11:1 Compound 22 fenpropimorph 7:1 2:1 1:1 Compound 22 fenpyrazamine 3:11:1 1:3 Compound 22 fentin salt such as fentin acetate, fentin chlorideor 3:1 1:1 1:3 fentin hydroxide Compound 22 ferbam 30:1  10:1  4:1Compound 22 ferimzone 7:1 2:1 1:2 Compound 22 fluazinam 3:1 1:1 1:2Compound 22 fludioxonil 2:1 1:1 1:4 Compound 22 flumetover 3:1 1:1 1:2Compound 22 flumorph 3:1 1:1 1:3 Compound 22 fluopicolide 1:1 1:2 1:6Compound 22 fluopyram 3:1 1:1 1:3 Compound 22 fluoroimide 37:1  14:1 5:1 Compound 22 fluoxastrobin 1:1 1:2 1:6 Compound 22 fluquinconazole1:1 1:2 1:4 Compound 22 flusilazole 3:1 1:1 1:3 Compound 22 flusulfamide15:1  5:1 2:1 Compound 22 flutianil 1:1 1:2 1:6 Compound 22 flutolanil4:1 1:1 1:2 Compound 22 flutriafol 1:1 1:2 1:4 Compound 22 fluxapyroxad2:1 1:1 1:3 Compound 22 folpet 15:1 5:1 2:1 Compound 22 fosetyl-aluminum30:1  12:1  5:1 Compound 22 fuberidazole 11:1  4:1 2:1 Compound 22furalaxyl 1:1 1:2 1:6 Compound 22 furametpyr 15:1 5:1 2:1 Compound 22guazatine 15:1  5:1 2:1 Compound 22 hexaconazole 1:1 1:2 1:5 Compound 22hymexazol 75:1  25:1  9:1 Compound 22 imazalil 1:1 1:2 1:5 Compound 22imibenconazole 1:1 1:2 1:5 Compound 22 iminoctadine 15:1  4:1 1:1Compound 22 iodocalb 15:1  5:1 2:1 Compound 22 ipconazole 1:1 1:2 1:5Compound 22 iprobenfos 15:1  5:1 2:1 Compound 22 iprodione 15:1  5:1 2:1Compound 22 iprovalicarb 2:1 1:1 1:3 Compound 22 isoprothiolane 45:1 15:1  5:1 Compound 22 isopyrazam 2:1 1:1 1:3 Compound 22 isotianil 2:11:1 1:3 Compound 22 kasugamycin 1:2 1:7  1:24 Compound 22kresoxim-methyl 2:1 1:1 1:4 Compound 22 mancozeb 22:1  7:1 3:1 Compound22 mandipropamid 2:1 1:1 1:4 Compound 22 maneb 22:1  7:1 3:1 Compound 22mepanipyrim 6:1 2:1 1:1 Compound 22 mepronil 1:1 1:2 1:6 Compound 22meptyldinocap 2:1 1:1 1:3 Compound 22 metalaxyl 1:1 1:2 1:6 Compound 22metalaxyl-M 1:1 1:4  1:12 Compound 22 metconazole 1:1 1:2 1:6 Compound22 methasulfocalb 15:1  5:1 2:1 Compound 22 metiram 15:1  5:1 2:1Compound 22 metominostrobin 3:1 1:1 1:3 Compound 22 metrafenone 2:1 1:11:4 Compound 22 myclobutanil 1:1 1:3 1:8 Compound 22 naftifine 15:1  5:12:1 Compound 22 neo-asozin (ferric methanearsonate) 15:1  5:1 2:1Compound 22 nuarimol 3:1 1:1 1:3 Compound 22 octhilinone 15:1  4:1 1:1Compound 22 ofurace 1:1 1:2 1:6 Compound 22 orysastrobin 3:1 1:1 1:3Compound 22 oxadixyl 1:1 1:2 1:6 Compound 22 oxolinic acid 7:1 2:1 1:2Compound 22 oxpoconazole 1:1 1:2 1:5 Compound 22 oxycarboxin 4:1 1:1 1:2Compound 22 oxytetracycline 3:1 1:1 1:3 Compound 22 pefurazoate 15:1 5:1 2:1 Compound 22 penconazole 1:2 1:6  1:15 Compound 22 pencycuron11:1  4:1 2:1 Compound 22 penthiopyrad 2:1 1:1 1:3 Compound 22phosphorous acid or a salt thereof 15:1  6:1 2:1 Compound 22 phthalide15:1  6:1 2:1 Compound 22 picoxystrobin 1:1 1:2 1:5 Compound 22piperalin 3:1 1:1 1:3 Compound 22 polyoxin 3:1 1:1 1:3 Compound 22probenazole 3:1 1:1 1:3 Compound 22 prochloraz 7:1 2:1 1:2 Compound 22procymidone 11:1  4:1 2:1 Compound 22 propamocarb orpropamocarb-hydrochloride 10:1  4:1 2:1 Compound 22 propiconazole 1:11:2 1:5 Compound 22 propineb 11:1  4:1 2:1 Compound 22 proquinazid 1:11:3  1:12 Compound 22 prothiocarb 3:1 1:1 1:3 Compound 22prothioconazole 1:1 1:2 1:5 Compound 22 pyraclostrobin 2:1 1:1 1:4Compound 22 pyrametostrobin 2:1 1:1 1:4 Compound 22 pyraoxystrobin 2:11:1 1:4 Compound 22 pyrazophos 15:1  4:1 1:1 Compound 22 pyribencarb 4:11:1 1:2 Compound 22 pyributicarb 15:1  4:1 1:1 Compound 22 pyrifenox 3:11:1 1:3 Compound 22 pyrimethanil 3:1 1:1 1:2 Compound 22 pyriofenone 2:11:1 1:4 Compound 22 pyroquilon 3:1 1:1 1:3 Compound 22 pyrrolnitrin15:1  5:1 2:1 Compound 22 quinomethionate 15:1  5:1 2:1 Compound 22quinoxyfen 1:1 1:2 1:6 Compound 22 quintozene 15:1  5:1 2:1 Compound 22silthiofam 2:1 1:1 1:4 Compound 22 simeconazole 1:1 1:2 1:5 Compound 22spiroxamine 5:1 2:1 1:2 Compound 22 streptomycin 3:1 1:1 1:3 Compound 22sulfur 75:1  25:1  9:1 Compound 22 tebuconazole 1:1 1:2 1:5 Compound 22tebufloquin 3:1 1:1 1:3 Compound 22 tecloftalam 15:1  5:1 2:1 Compound22 tecnazene 15:1  5:1 2:1 Compound 22 terbinafine 15:1  5:1 2:1Compound 22 tetraconazole 1:1 1:2 1:5 Compound 22 thiabendazole 11:1 4:1 2:1 Compound 22 thifluzamide 3:1 1:1 1:3 Compound 22 thiophanate11:1  4:1 2:1 Compound 22 thiophanate-methyl 11:1  4:1 2:1 Compound 22thiram 37:1  14:1  5:1 Compound 22 tiadinil 2:1 1:1 1:3 Compound 22tolclofos-methyl 37:1  14:1  5:1 Compound 22 tolylfluanid 15:1  5:1 2:1Compound 22 triadimefon 1:1 1:2 1:5 Compound 22 triadimenol 1:1 1:2 1:5Compound 22 triazoxide 15:1  5:1 2:1 Compound 22 tricyclazole 3:1 1:11:3 Compound 22 tridemorph 7:1 2:1 1:1 Compound 22 trifloxystrobin 2:11:1 1:4 Compound 22 triflumizole 3:1 1:1 1:3 Compound 22 triforine 3:11:1 1:3 Compound 22 trimorphamide 7:1 2:1 1:2 Compound 22 triticonazole1:1 1:2 1:5 Compound 22 uniconazole 1:1 1:2 1:5 Compound 22 validamycin3:1 1:1 1:3 Compound 22 valifenalate (valiphenal) 2:1 1:1 1:4 Compound22 vinclozolin 15:1  6:1 2:1 Compound 22 zineb 37:1  14:1  5:1 Compound22 ziram 37:1  14:1  5:1 Compound 22 zoxamide 2:1 1:1 1:4 Compound 225-chloro-6-(2,4,6-trifluorophenyl)-7-(4-methylpiperidin- 1:1 1:2 1:61-yl)[1,2,4]triazolo[1,5-a]pyrimidine Compound 22 Penflufen(N-[2-(1,3-dimethylbutyl)phenyl]-5-fluoro- 2:1 1:1 1:31,3-dimethyl-1H-pyrazole-4-carboxamide) Compound 22N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3- 2:1 1:1 1:4methoxyphenyl]ethyl]-3-methyl-2-[(methylsulfonyl) amino]butanamideCompound 22 N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3- 2:1 1:11:4 methoxyphenyl]ethyl]-3-methyl-2-[(ethylsulfonyl) amino]butanamideCompound 22 2-butoxy-6-iodo-3-propyl-4H-1-benzopyran-4-one 1:1 1:3  1:12Compound 22 3-[5-(4-chlorophenyl)-2,3-dimethyl-3-isoxazolidinyl] 3:1 1:11:3 pyridine Compound 22 4-fluorophenylN-[1-[[[1-(4-cyanophenyl)ethyl]sulfonyl] 2:1 1:1 1:4methyl]propyl]carbamate Compound 22N-[[(cyclopropylmethoxy)amino][6-(difluoromethoxy)- 1:2 1:7  1:242,3-difluorophenyl]methylene]benzeneacetamide Compound 22α-[methoxyimino]-N-methyl-2-[[[1-[3-(trifluoromethyl) 3:1 1:1 1:3phenyl]ethoxy]imino]methyl]-benzeneacetamide Compound 22N′-[4-[4-chloro-3-(trifluoromethyl)phenoxy]-2,5- 3:1 1:1 1:3dimethylphenyl]-N-ethyl-N-methylmethanimidamide Compound 22N-(4-chloro-2-nitrophenyl)-N-ethyl-4-methyl- 3:1 1:1 1:3benzenesulfonamide Compound 222-[[[3-(2,6-dichlorophenyl)-1-methyl-2-propen-1- 3:1 1:1 1:3ylidene]amino]oxy]methyl]-α-(methoxyimino)-N- methylbenzeneacetamideCompound 22 pentyl N-[4-[[[[(1-methyl-1H-tetrazol-5-yl)phenyl- 3:1 1:11:3 methylene]amino]oxy]methyl]-2-thiazolyl]carbamate Compound 22 pentylN-[6-[[[[(1-methyl-1H-tetrazol-5-yl)phenyl- 3:1 1:1 1:3methylene]amino]oxy]methyl]-2-pyridinyl]carbamate (*) Ratios ofComponent (b) relative to Component (a) by weight.

Tables A2 through A54 are each constructed the same as Table A1 aboveexcept that entries below the “Component (a)” column heading arereplaced with the respective Component (a) Column Entry shown below.Thus, for example, in Table A2 the entries below the “Component (a)”column heading all recite “Compound 18”, and the first line below thecolumn headings in Table A2 specifically discloses a mixture of Compound18 with acibenzolar-S-methyl. Tables A3 through A54 are constructedsimilarly.

Table Number Component (a) Column Entries A2 Compound 18 A3 Compound 23A4 Compound 24 A5 Compound 36 A6 Compound 41 A7 Compound 45 A8 Compound87 A9 Compound 91 A10 Compound 118 A11 Compound 139 A12 Compound 148 A13Compound 172 A14 Compound 175 A15 Compound 193 A16 Compound 232 A17Compound 265 A18 Compound 266 A19 Compound 284 A20 Compound 286 A21Compound 287 A22 Compound 292 A23 Compound 297 A24 Compound 332 A25Compound 336 A26 Compound 343 A27 Compound 346 A28 Compound 349 A29Compound 351 A30 Compound 352 A31 Compound 357 A32 Compound 358 A33Compound 360 A34 Compound 361 A35 Compound 364 A36 Compound 365 A37Compound 367 A38 Compound 368 A39 Compound 369 A40 Compound 372 A41Compound 373 A42 Compound 374 A43 Compound 375 A44 Compound 376 A45Compound 377 A46 Compound 378 A47 Compound 379 A48 Compound 380 A49Compound 381 A50 Compound 382 A51 Compound 383 A52 Compound 384 A53Compound 385 A54 Compound 386

Table B1 lists specific combinations of a Component (b) compound withComponent (a) illustrative of the mixtures, compositions and methods ofthe present invention. The first column of Table B1 lists the specificComponent (b) compound (e.g., “acibenzolar-S-methyl” in the first line).The second, third and fourth columns of Table B1 lists ranges of weightratios for rates at which the Component (b) compound is typicallyapplied to a field-grown crop relative to Component (a) (e.g., “2:1 to1:180” of acibenzolar-S-methyl relative to Component (a) by weight).Thus, for example, the first line of Table B1 specifically discloses thecombination of acibenzolar-S-methyl with Component (a) is typicallyapplied in a weight ratio between 2:1 to 1:180. The remaining lines ofTable B1 are to be construed similarly. Table B1 thus supplements thespecific ratios disclosed in Tables A1 through A54 with ranges of ratiosfor these combinations.

TABLE B1 More Most Typical Typical Typical Weight Weight WeightComponent (b) Ratio Ratio Ratio acibenzolar-S-methyl   2:1 to 1:180  1:1 to 1:60   1:1 to 1:18 aldimorph  30:1 to 1:3  10:1 to 1:1   7:1 to1:1 ametoctradin   9:1 to 1:18   3:1 to 1:6   3:1 to 1:3 amisulbrom  6:1 to 1:18   2:1 to 1:6   1:1 to 1:6 anilazine  90:1 to 2:1  30:1 to4:1  22:1 to 4:1 azaconazole   7:1 to 1:18   2:1 to 1:6   2:1 to 1:4azoxystrobin   9:1 to 1:12   3:1 to 1:4   3:1 to 1:3 benalaxyl   4:1 to1:18   1:1 to 1:6   1:1 to 1:6 benalaxyl-M   4:1 to 1:36   1:1 to 1:12  1:1 to 1:8 benodanil  18:1 to 1:6   6:1 to 1:2   4:1 to 1:2 benomyl 45:1 to 1:4  15:1 to 1:1  11:1 to 1:1 benthiavalicarb or   2:1 to 1:36  1:1 to 1:12   1:1 to 1:12 benthiavalicarb-     isopropyl    bethoxazin 150:1 to 1:36  50:1 to 1:12  15:1 to 2:1 binapacryl 150:1 to1:36  50:1 to 1:12  15:1 to 2:1 biphenyl 150:1 to 1:36  50:1 to 1:12 15:1 to 2:1 bitertanol  15:1 to 1:5   5:1 to 1:2   3:1 to 1:2 bixafen 12:1 to 1:9   4:1 to 1:3   2:1 to 1:3 blasticidin-S   3:1 to 1:90   1:1to 1:30   1:4 to 1:30 boscalid  18:1 to 1:6   6:1 to 1:2   4:1 to 1:2bromuconazole  15:1 to 1:9   5:1 to 1:3   3:1 to 1:3 bupirimate   3:1 to1:90  1:1 to 1:30   1:3 to 1:30 captafol  90:1 to 1:4  30:1 to 1:2  15:1to 2:1 captan  90:1 to 1:4  30:1 to 1:2  15:1 to 2:1 carbendazim  45:1to 1:4  15:1 to 1:2  11:1 to 2:1 carboxin  18:1 to 1:6   6:1 to 1:2  4:1 to 1:2 carpropamid  15:1 to 1:9   5:1 to 1:3   3:1 to 1:3chloroneb 300:1 to 2:1 100:1 to 4:1 100:1 to 14:1 chlorothalonil  90:1to 1:4  30:1 to 1:2  15:1 to 2:1 chlozolinate  45:1 to 1:2  15:1 to 2:1 11:1 to 2:1 clotrimazole  15:1 to 1:9   5:1 to 1:3   3:1 to 1:3 coppersalts such as 450:1 to 1:1 150:1 to 4:1  45:1 to 5:1 Bordeaux mixture(tribasic copper sulfate), copper oxychloride, copper sulfate and copperhydroxide cyazofamid  4:1 to 1:18  1:1 to 1:6  1:1 to 1:6 cyflufenamid 1:1 to 1:90  1:2 to 1:30  1:2 to 1:24 cymoxanil  6:1 to 1:18  2:1 to1:6  1:1 to 1:5 cyproconazole  4:1 to 1:18  1:1 to 1:6  1:1 to 1:6cyprodinil  22:1 to 1:9  7:1 to 1:3  4:1 to 1:2 dichlofluanid 150:1 to1:36  50:1 to 1:12  15:1 to 2:1 diclocymet 150:1 to 1:36  50:1 to 1:12 15:1 to 2:1 diclomezine  15:1 to 1:9   5:1 to 1:3   3:1 to 1:3 dicloran150:1 to 1:36  50:1 to 1:12  15:1 to 2:1 diethofencarb  22:1 to 1:9  7:1 to 1:3   7:1 to 1:2 difenoconazole   4:1 to 1:36   1:1 to 1:12  1:1 to 1:12 diflumetorim 150:1 to 1:36  50:1 to 1:12  15:1 to 2:1dimethirimol   3:1 to 1:90   1:1 to 1:30   1:3 to 1:30 dimethomorph  9:1 to 1:6   3:1 to 1:2   3:1 to 1:2 dimoxystrobin   9:1 to 1:18   3:1to 1:6   2:1 to 1:4 diniconazole   3:1 to 1:36   1:1 to 1:12   1:1 to1:8 diniconazole M   3:1 to 1:90   1:1 to 1:30   1:1 to 1:12 dinocap  7:1 to 1:9   2:1 to 1:3   2:1 to 1:3 dithianon  15:1 to 1:4   5:1 to1:2   5:1 to 1:2 dodemorph  30:1 to 1:3  10:1 to 1:1   7:1 to 1:1 dodine 30:1 to 1:2  10:1 to 2:1  10:1 to 2:1 edifenphos  30:1 to 1:9  10:1 to1:3   3:1 to 1:3 enestroburin   9:1 to 1:18   3:1 to 1:6   2:1 to 1:4epoxiconazole   3:1 to 1:36   1:1 to 1:12   1:1 to 1:7 ethaboxam   7:1to 1:9   2:1 to 1:3   2:1 to 1:3 ethirimol  30:1 to 1:3  10:1 to 1:1  7:1 to 1:1 etridiazole  30:1 to 1:9  10:1 to 1:3   7:1 to 1:2famoxadone   9:1 to 1:18   3:1 to 1:6   2:1 to 1:4 fenamidone   6:1 to1:18   2:1 to 1:6   2:1 to 1:4 fenarimol   3:1 to 1:90   1:1 to 1:30  1:2 to 1:24 fenbuconazole   3:1 to 1:30   1:1 to 1:10   1:1 to 1:10fenfuram  18:1 to 1:6   6:1 to 1:2   4:1 to 1:2 fenhexamid  30:1 to 1:2 10:1 to 2:1  10:1 to 2:1 fenoxanil 150:1 to 1:36  50:1 to 1:12  15:1 to1:1 fenpiclonil  75:1 to 1:9  25:1 to 1:3  15:1 to 2:1 fenpropidin  30:1to 1:3  10:1 to 1:1   7:1 to 1:1 fenpropimorph  30:1 to 1:3  10:1 to 1:1  7:1 to 1:1 fenpyrazamine 100:1 to 1:100  10:1 to 1:10   3:1 to 1:3fentin salt such as the  15:1 to 1:9   5:1 to 1:3   3:1 to 1:3 acetate,chloride or hydroxide ferbam 300:1 to 1:2 100:1 to 2:1  30:1 to 4:1ferimzone  30:1 to 1:5  10:1 to 1:2   7:1 to 1:2 fluazinam  22:1 to 1:5  7:1 to 1:2   3:1 to 1:2 fludioxonil   7:1 to 1:12   2:1 to 1:4   2:1to 1:4 flumetover   9:1 to 1:6   3:1 to 1:2   3:1 to 1:2 flumorph   9:1to 1:18   3:1 to 1:6   3:1 to 1:3 fluopicolide   3:1 to 1:18   1:1 to1:6   1:1 to 1:6 fluopyram  15:1 to 1:90   5:1 to 1:30   3:1 to 1:3fluoromide 150:1 to 2:1  50:1 to 4:1  37:1 to 5:1 fluoxastrobin   4:1 to1:18   1:1 to 1:6   1:1 to 1:6 fluquinconazole   4:1 to 1:12   1:1 to1:4   1:1 to 1:4 flusilazole  15:1 to 1:9   5:1 to 1:3   3:1 to 1:3flusulfamide  90:1 to 1:2  30:1 to 2:1  15:1 to 2:1 flutianil   7:1 to1:36   2:1 to 1:12   1:1 to 1:6 flutolanil  18:1 to 1:6   6:1 to 1:2  4:1 to 1:2 flutriafol   4:1 to 1:12   1:1 to 1:4   1:1 to 1:4fluxapyroxad  12:1 to 1:9   4:1 to 1:3   2:1 to 1:3 folpet  90:1 to 1:4 30:1 to 1:2  15:1 to 2:1 fosetyl-aluminum 225:1 to 2:1  75:1 to 5:1 30:1 to 5:1 fuberidazole  45:1 to 1:4  15:1 to 1:2  11:1 to 2:1furalaxyl  15:1 to 1:45   5:1 to 1:15   1:1 to 1:6 furametpyr 150:1 to1:36  50:1 to 1:12  15:1 to 2:1 guazatine or iminoctadine 150:1 to 1:36 50:1 to 1:12  15:1 to 2:1 hexaconazole  15:1 to 1:36   5:1 to 1:12  1:1 to 1:5 hymexazol 225:1 to 2:1  75:1 to 4:1  75:1 to 9:1 imazalil 7:1 to 1:18   2:1 to 1:6   1:1 to 1:5 imibenconazole  15:1 to 1:36  5:1 to 1:12   1:1 to 1:5 iodocarb 150:1 to 1:36  50:1 to 1:12  15:1 to2:1 ipconazole  15:1 to 1:36   5:1 to 1:12   1:1 to 1:5 iprobenfos 150:1to 1:36  50:1 to 1:12  15:1 to 2:1 iprodione 120:1 to 1:2  40:1 to 2:1 15:1 to 2:1 iprovalicarb  9:1 to 1:9   3:1 to 1:3   2:1 to 1:3isoprothiolane 150:1 to 2:1  50:1 to 4:1  45:1 to 5:1 isopyrazam  12:1to 1:9   4:1 to 1:3   2:1 to 1:3 isotianil  12:1 to 1:9   4:1 to 1:3  2:1 to 1:3 kasugamycin  7:1 to 1:90   2:1 to 1:30   1:2 to 1:24kresoxim-methyl  7:1 to 1:18   2:1 to 1:6   2:1 to 1:4 mancozeb 180:1 to1:3  60:1 to 2:1  22:1 to 3:1 mandipropamid  6:1 to 1:18   2:1 to 1:6 2:1 to 1:4 maneb 180:1 to 1:3  60:1 to 2:1  22:1 to 3:1 mepanipyrim 18:1 to 1:3  6:1 to 1:1  6:1 to 1:1 mepronil  7:1 to 1:36  2:1 to 1:12 1:1 to 1:6 meptyldinocap  7:1 to 1:9  2:1 to 1:3  2:1 to 1:3 metalaxyl 15:1 to 1:45  5:1 to 1:15  1:1 to 1:6 metalaxyl-M  7:1 to 1:90  2:1 to1:30  1:1 to 1:12 metconazole  3:1 to 1:18  1:1 to 1:6  1:1 to 1:6methasulfocarb 150:1 to 1:36  50:1 to 1:12  15:1 to 1:1 metiram 150:1 to1:36  50:1 to 1:12  15:1 to 1:1 metominostrobin   9:1 to 1:12   3:1 to1:4   3:1 to 1:3 metrafenone   6:1 to 1:12   2:1 to 1:4   2:1 to 1:4myclobutanil   5:1 to 1:26  1:1 to 1:9   1:1 to 1:8 naftifine 150:1 to1:36  50:1 to 1:12  15:1 to 2:1 neo-asozin (ferric 150:1 to 1:36  50:1to 1:12  15:1 to 2:1 methanearsonate) nuarimol  15:1 to 1:9  5:1 to 1:3 3:1 to 1:3 octhilinone 150:1 to 1:36  50:1 to 1:12  15:1 to 1:1 ofurace 15:1 to 1:45   5:1 to 1:15   1:1 to 1:6 orysastrobin   9:1 to 1:12  3:1 to 1:4   3:1 to 1:3 oxadixyl  15:1 to 1:45   5:1 to 1:15   1:1 to1:6 oxolinic acid  30:1 to 1:9  10:1 to 1:3   7:1 to 1:2 oxpoconazole 15:1 to 1:36   5:1 to 1:12   1:1 to 1:5 oxycarboxin  18:1 to 1:6   6:1to 1:2   4:1 to 1:2 oxytetracycline  15:1 to 1:9   5:1 to 1:3   3:1 to1:3 pefurazoate 150:1 to 1:36  50:1 to 1:12  15:1 to 2:1 penconazole 1:1 to 1:45  1:2 to 1:15  1:2 to 1:15 pencycuron 150:1 to 1:2  50:1 to2:1  11:1 to 2:1 penthiopyrad  12:1 to 1:9   4:1 to 1:3   2:1 to 1:3phosphorous acid 150:1 to 1:36  50:1 to 1:12  15:1 to 2:1 and saltsthereof     phthalide 150:1 to 1:36  50:1 to 1:12  15:1 to 2:1picoxystrobin   7:1 to 1:18   2:1 to 1:6   1:1 to 1:5 piperalin  15:1 to1:9   5:1 to 1:3   3:1 to 1:3 polyoxin  15:1 to 1:9   5:1 to 1:3   3:1to 1:3 probenazole  15:1 to 1:9   5:1 to 1:3   3:1 to 1:3 prochloraz 22:1 to 1:4   7:1 to 1:1   7:1 to 1:2 procymidone  45:1 to 1:3  15:1 to1:1  11:1 to 2:1 propamocarb or  30:1 to 1:2  10:1 to 2:1  10:1 to 2:1propamocarb- hydrochloride propiconazole  4:1 to 1:18  1:1 to 1:6  1:1to 1:5 propineb  45:1 to 1:2  15:1 to 2:1  11:1 to 2:1 proquinazid  3:1to 1:36  1:1 to 1:12  1:1 to 1:12 prothiocarb  9:1 to 1:18  3:1 to 1:6 3:1 to 1:3 prothioconazole  6:1 to 1:18  2:1 to 1:6  1:1 to 1:5pyraclostrobin  9:1 to 1:18  3:1 to 1:6  2:1 to 1:4 pyrametostrobin  9:1to 1:18  3:1 to 1:6  2:1 to 1:4 pyraoxystrobin  9:1 to 1:18  3:1 to 1:6 2:1 to 1:4 pyrazophos 150:1 to 1:36  50:1 to 1:12  15:1 to 1:1pyribencarb  15:1 to 1:6  5:1 to 1:2  4:1 to 1:2 pyrifenox  15:1 to 1:9 5:1 to 1:3  3:1 to 1:3 pyrimethanil  30:1 to 1:6  10:1 to 1:2  3:1 to1:2 pyriofenone  6:1 to 1:12   2:1 to 1:4  2:1 to 1:4 pyroquilon  15:1to 1:9   5:1 to 1:3  3:1 to 1:3 pyrrolnitrin 150:1 to 1:36  50:1 to 1:12 15:1 to 2:1 quinmethionate 150:1 to 1:36  50:1 to 1:12  15:1 to 2:1quinoxyfen  4:1 to 1:18   1:1 to 1:6   1:1 to 1:6 quintozene 150:1 to1:36  50:1 to 1:12  15:1 to 2:1 silthiofam   7:1 to 1:18   2:1 to 1:6 2:1 to 1:4 simeconazole  15:1 to 1:36   5:1 to 1:12  1:1 to 1:5spiroxamine  22:1 to 1:4   7:1 to 1:2  5:1 to 1:2 streptomycin  15:1 to1:9   5:1 to 1:3  3:1 to 1:3 sulfur 300:1 to 3:1 100:1 to 9:1  75:1 to9:1 tebuconazole  7:1 to 1:18   2:1 to 1:6   1:1 to 1:5 tebufloquin100:1 to 1:100  10:1 to 1:10   3:1 to 1:3 tecloftalam 150:1 to 1:36 50:1 to 1:12  15:1 to 2:1 tecnazene 150:1 to 1:36  50:1 to 1:12  15:1to 2:1 terbinafine 150:1 to 1:36  50:1 to 1:12  15:1 to 2:1tetraconazole  15:1 to 1:36  5:1 to 1:12  1:1 to 1:5 thiabendazole  45:1to 1:4  15:1 to 1:2  11:1 to 2:1 thifluzamide  15:1 to 1:9   5:1 to 1:3  3:1 to 1:3 thiophanate  45:1 to 1:3  15:1 to 2:1  11:1 to 2:1thiophanate-methyl  45:1 to 1:3  15:1 to 2:1  11:1 to 2:1 thiram 150:1to 1:2  50:1 to 2:1  37:1 to 5:1 tiadinil  12:1 to 1:9  4:1 to 1:3  2:1to 1:3 tolclofos-methyl 150:1 to 1:2  50:1 to 2:1  37:1 to 5:1tolylfluanid 150:1 to 1:36  50:1 to 1:12  15:1 to 2:1 triadimefon  15:1to 1:36  5:1 to 1:12  1:1 to 1:5 triadimenol  15:1 to 1:36  5:1 to 1:12 1:1 to 1:5 triazoxide 150:1 to 1:36  50:1 to 1:12  15:1 to 2:1tricyclazole  15:1 to 1:9   5:1 to 1:3  3:1 to 1:3 tridemorph  30:1 to1:3  10:1 to 1:1  7:1 to 1:1 trifloxystrobin   6:1 to 1:18   2:1 to 1:6 2:1 to 1:4 triflumizole  15:1 to 1:9   5:1 to 1:3  3:1 to 1:3 triforine 15:1 to 1:9   5:1 to 1:3  3:1 to 1:3 trimorphamide  45:1 to 1:9  15:1to 1:3  7:1 to 1:2 triticonazole  15:1 to 1:36   5:1 to 1:12  1:1 to 1:5uniconazole  15:1 to 1:36   5:1 to 1:12  1:1 to 1:5 validamycin 150:1 to1:36  50:1 to 1:12  3:1 to 1:3 valifenalate (valiphenal)  6:1 to 1:18  2:1 to 1:6  2:1 to 1:4 vinclozolin 120:1 to 1:2  40:1 to 2:1  15:1 to2:1 zineb 150:1 to 1:2  50:1 to 2:1  37:1 to 5:1 ziram 150:1 to 1:2 50:1 to 2:1  37:1 to 5:1 zoxamide  6:1 to 1:18   2:1 to 1:6  2:1 to 1:45-chloro-6-(2,4,6-  15:1 to 1:36   5:1 to 1:12  1:1 to 1:6trifluorophenyl)-7-(4- methylpiperidin-1- yl)[1,2,4]triazolo[1,5-a]pyrimidine penflufen (N-[2-(1,3-  12:1 to 1:9   4:1 to 1:3   2:1 to1:3 dimethylbutyl)phenyl]- 5-fluoro-1,3- dimethyl-1H-pyrazole-4-carboxamide) N-[2-[4-[[3-(4-  6:1 to 1:18  2:1 to 1:6  2:1 to 1:4chlorophenyl)-2-propyn-1- yl]oxy]-3- methoxyphenyl]ethyl]- 3-methyl-2-[methylsulfonyl)ami- no]butanamide N-[2-[4-[[3-(4-  6:1 to 1:18  2:1to 1:6  2:1 to 1:4 chlorophenyl)-2-propyn-1- yl]oxy]-3-methoxyphenyl]ethyl]- 3-methyl- 2-[(ethylsulfonyl)ami- no]butanamide2-butoxy-6-iodo-  3:1 to 1:36  1:1 to 1:12  1:1 to 1:12 3-propyl-4H-1-benzopyran-4-one 3-[5-(4-chlorophenyl)-  15:1 to 1:9  5:1 to 1:3  3:1 to1:3 2,3-dimethyl-3- isoxazolidinyl]pyridine 4-fluorophenyl N-[1-[[[1-(4- 6:1 to 1:18  2:1 to 1:6  2:1 to 1:4 cyanophenyl)ethyl]sul-fonyl]methyl]propyl] carbamate N-[[(cyclopropyl-  1:1 to 1:90  1:2 to1:30  1:2 to 1:24 methoxy)amino][6- (difluoromethoxy)-2,3-difluorophenyl]me- thylene]benzene- acetamide α-[methoxyimino]-N-  9:1to 1:18  3:1 to 1:6  3:1 to 1:3 methyl-2-[[[1-[3- (trifluoromethyl)phe-nyl]ethoxy]imino]- methyl]benzeneacetamide N′-[4-[4-chloro-3-  15:1 to1:18   5:1 to 1:6   3:1 to 1:3 (trifluoromethyl)phenoxy]-2,5-dimethylphenyl]- N-ethyl-N- methylmethanimidamide N-(4-chloro-2- 15:1 to 1:18   5:1 to 1:6   3:1 to 1:3 nitrophenyl)-N-ethyl-4-methylbenzenesulfonamide 2-[[[3-(2,6-dichlorophenyl)-  9:1 to 1:18  3:1to 1:6  3:1 to 1:3 1-methyl-2- propen-1-ylidene]ami- no]oxy]methyl]-α-(methoxyimino)-N- methylbenzeneacetamide pentyl N-[4-[[[[(1-methyl-  9:1to 1:18  3:1 to 1:6  3:1 to 1:3 1H-tetrazol-5- yl)phenylmethy-lene]amino]oxy]methyl]-2- thiazolyl]carbamate pentyl N-[6-[[[[(1-methyl- 9:1 to 1:18  3:1 to 1:6  3:1 to 1:3 1H-tetrazol-5-yl)phenylmethylene]ami- no]oxy]methyl]-2- pyridinyl]carbamate

As already noted, the present invention includes embodiments wherein inthe composition comprising components (a) and (b), component (b)comprises at least one fungicide from each of two groups selected from(b1) through (b46). Tables C1 through C54 list specific mixtures(compound numbers refer to compounds in Index Table A) to illustrateembodiments wherein component (b) includes at least one fungicide fromeach of two groups selected from (b1) through (b46). In Table C1, eachline below the column headings “Component (a)” and “Component (b)”specifically discloses a mixture of Component (a), which is Compound 22,with at least two Component (b) fungicides. The entries under theheading “Illustrative Ratios” disclose three specific weight ratios ofComponent (a) to each Component (b) fungicide in sequence for thedisclosed mixture. For example, the first line discloses a mixture ofCompound 22 with cyproconazole and azoxystrobin and lists weight ratiosof Compound 22 to cyproconazole to azoxystrobin of 1:1:1, 2:1:1 or3:1:1.

TABLE C1 Component (a) Component (b) Illustrative Ratios(*) Compound 22cyproconazole azoxystrobin 1:1:1 2:1:1 3:1:1 Compound 22 cyproconazolekresoxim-methyl 1:1:1 2:1:1 3:1:1 Compound 22 cyproconazolepicoxystrobin 1:1:1 2:1:1 3:1:1 Compound 22 cyproconazole pyraclostrobin1:1:1 2:1:1 3:1:1 Compound 22 cyproconazole trifloxystrobin 1:1:1 2:1:13:1:1 Compound 22 cyproconazole bixafen 1:1:2 2:1:2 3:1:2 Compound 22cyproconazole boscalid 1:1:2 2:1:2 3:1:2 Compound 22 cyproconazolecyflufenamid 1:2:1 2:2:1 3:2:1 Compound 22 cyproconazole fluopyram 1:1:22:1:2 3:1:2 Compound 22 cyproconazole isopyrazam 1:1:2 2:1:2 3:1:2Compound 22 cyproconazole metrafenone 1:1:2 2:1:2 3:1:2 Compound 22cyproconazole penthiopyrad 1:1:2 2:1:2 3:1:2 Compound 22 cyproconazoleproquinazid 1:1:1 2:1:1 3:1:1 Compound 22 cyproconazole quinoxyfen 1:1:12:1:1 3:1:1 Compound 22 cyproconazole sedaxane 1:1:2 2:1:2 3:1:2Compound 22 cyproconazole picoxystrobin proquinazid 1:1:1:1 2:1:1:13:1:1:1 Compound 22 cyproconazole trifloxystrobin proquinazid 1:1:1:12:1:1:1 3:1:1:1 Compound 22 difenconazole azoxystrobin 1:1:1 2:1:1 3:1:1Compound 22 difenconazole kresoxim-methyl 1:1:1 2:1:1 3:1:1 Compound 22difenconazole picoxystrobin 1:1:1 2:1:1 3:1:1 Compound 22 difenconazolepyraclostrobin 1:1:1 2:1:1 3:1:1 Compound 22 difenconazoletrifloxystrobin 1:1:1 2:1:1 3:1:1 Compound 22 difenconazole bixafen1:1:2 2:1:2 3:1:2 Compound 22 difenconazole boscalid 1:1:2 2:1:2 3:1:2Compound 22 difenconazole cyflufenamid 1:2:1 2:2:1 3:2:1 Compound 22difenconazole fluopyram 1:1:2 2:1:2 3:1:2 Compound 22 difenconazoleisopyrazam 1:1:2 2:1:2 3:1:2 Compound 22 difenconazole metrafenone 1:1:22:1:2 3:1:2 Compound 22 difenconazole penthiopyrad 1:1:2 2:1:2 3:1:2Compound 22 difenconazole proquinazid 1:1:1 2:1:1 3:1:1 Compound 22difenconazole quinoxyfen 1:1:1 2:1:1 3:1:1 Compound 22 difenconazolesedaxane 1:1:2 2:1:2 3:1:2 Compound 22 difenconazole picoxystrobinproquinazid 1:1:1:1 2:1:1:1 3:1:1:1 Compound 22 difenconazoletrifloxystrobin proquinazid 1:1:1:1 2:1:1:1 3:1:1:1 Compound 22epoxiconazole azoxystrobin 1:1:1 2:1:1 3:1:1 Compound 22 epoxiconazolekresoxim-methyl 1:1:1 2:1:1 3:1:1 Compound 22 epoxiconazolepicoxystrobin 1:1:1 2:1:1 3:1:1 Compound 22 epoxiconazole pyraclostrobin1:1:1 2:1:1 3:1:1 Compound 22 epoxiconazole trifloxystrobin 1:1:1 2:1:13:1:1 Compound 22 epoxiconazole bixafen 1:1:2 2:1:2 3:1:2 Compound 22epoxiconazole boscalid 1:1:2 2:1:2 3:1:2 Compound 22 epoxiconazolecyflufenamid 1:2:1 2:2:1 3:2:1 Compound 22 epoxiconazole fluopyram 1:1:22:1:2 3:1:2 Compound 22 epoxiconazole isopyrazam 1:1:2 2:1:2 3:1:2Compound 22 epoxiconazole metrafenone 1:1:2 2:1:2 3:1:2 Compound 22epoxiconazole penthiopyrad 1:1:2 2:1:2 3:1:2 Compound 22 epoxiconazoleproquinazid 1:1:1 2:1:1 3:1:1 Compound 22 epoxiconazole quinoxyfen 1:1:12:1:1 3:1:1 Compound 22 epoxiconazole sedaxane 1:1:2 2:1:2 3:1:2Compound 22 epoxiconazole picoxystrobin proquinazid 1:1:1:1 2:1:1:13:1:1:1 Compound 22 epoxiconazole trifloxystrobin proquinazid 1:1:1:12:1:1:1 3:1:1:1 Compound 22 metconazole azoxystrobin 1:1:1 2:1:1 3:1:1Compound 22 metconazole kresoxim-methyl 1:1:1 2:1:1 3:1:1 Compound 22metconazole picoxystrobin 1:1:1 2:1:1 3:1:1 Compound 22 metconazolepyraclostrobin 1:1:1 2:1:1 3:1:1 Compound 22 metconazole trifloxystrobin1:1:1 2:1:1 3:1:1 Compound 22 metconazole bixafen 1:1:2 2:1:2 3:1:2Compound 22 metconazole boscalid 1:1:2 2:1:2 3:1:2 Compound 22metconazole cyflufenamid 1:2:1 2:2:1 3:2:1 Compound 22 metconazolefluopyram 1:1:2 2:1:2 3:1:2 Compound 22 metconazole isopyrazam 1:1:22:1:2 3:1:2 Compound 22 metconazole metrafenone 1:1:2 2:1:2 3:1:2Compound 22 metconazole penthiopyrad 1:1:2 2:1:2 3:1:2 Compound 22metconazole proquinazid 1:1:1 2:1:1 3:1:1 Compound 22 metconazolequinoxyfen 1:1:1 2:1:1 3:1:1 Compound 22 metconazole sedaxane 1:1:22:1:2 3:1:2 Compound 22 metconazole picoxystrobin proquinazid 1:1:1:12:1:1:1 3:1:1:1 Compound 22 metconazole trifloxystrobin proquinazid1:1:1:1 2:1:1:1 3:1:1:1 Compound 22 myclobutanil azoxystrobin 1:1:12:1:1 3:1:1 Compound 22 myclobutanil kresoxim-methyl 1:1:1 2:1:1 3:1:1Compound 22 myclobutanil picoxystrobin 1:1:1 2:1:1 3:1:1 Compound 22myclobutanil pyraclostrobin 1:1:1 2:1:1 3:1:1 Compound 22 myclobutaniltrifloxystrobin 1:1:1 2:1:1 3:1:1 Compound 22 myclobutanil bixafen 1:1:22:1:2 3:1:2 Compound 22 myclobutanil boscalid 1:1:2 2:1:2 3:1:2 Compound22 myclobutanil cyflufenamid 1:2:1 2:2:1 3:2:1 Compound 22 myclobutanilfluopyram 1:1:2 2:1:2 3:1:2 Compound 22 myclobutanil isopyrazam 1:1:22:1:2 3:1:2 Compound 22 myclobutanil metrafenone 1:1:2 2:1:2 3:1:2Compound 22 myclobutanil penthiopyrad 1:1:2 2:1:2 3:1:2 Compound 22myclobutanil proquinazid 1:1:1 2:1:1 3:1:1 Compound 22 myclobutanilquinoxyfen 1:1:1 2:1:1 3:1:1 Compound 22 myclobutanil sedaxane 1:1:22:1:2 3:1:2 Compound 22 myclobutanil picoxystrobin proquinazid 1:1:1:12:1:1:1 3:1:1:1 Compound 22 myclobutanil trifloxystrobin proquinazid1:1:1:1 2:1:1:1 3:1:1:1 Compound 22 prothioconazole azoxystrobin 1:1:12:1:1 3:1:1 Compound 22 prothioconazole kresoxim-methyl 1:1:1 2:1:13:1:1 Compound 22 prothioconazole picoxystrobin 1:1:1 2:1:1 3:1:1Compound 22 prothioconazole pyraclostrobin 1:1:1 2:1:1 3:1:1 Compound 22prothioconazole trifloxystrobin 1:1:1 2:1:1 3:1:1 Compound 22prothioconazole bixafen 1:1:2 2:1:2 3:1:2 Compound 22 prothioconazoleboscalid 1:1:2 2:1:2 3:1:2 Compound 22 prothioconazole cyflufenamid1:2:1 2:2:1 3:2:1 Compound 22 prothioconazole fluopyram 1:1:2 2:1:23:1:2 Compound 22 prothioconazole isopyrazam 1:1:2 2:1:2 3:1:2 Compound22 prothioconazole metrafenone 1:1:2 2:1:2 3:1:2 Compound 22prothioconazole penthiopyrad 1:1:2 2:1:2 3:1:2 Compound 22prothioconazole proquinazid 1:1:1 2:1:1 3:1:1 Compound 22prothioconazole quinoxyfen 1:1:1 2:1:1 3:1:1 Compound 22 prothioconazolesedaxane 1:1:2 2:1:2 3:1:2 Compound 22 prothioconazole picoxystrobinproquinazid 1:1:1:1 2:1:1:1 3:1:1:1 Compound 22 prothioconazoletrifloxystrobin proquinazid 1:1:1:1 2:1:1:1 3:1:1:1 Compound 22tebuconazole azoxystrobin 1:1:1 2:1:1 3:1:1 Compound 22 tebuconazolekresoxim-methyl 1:1:1 2:1:1 3:1:1 Compound 22 tebuconazole picoxystrobin1:1:1 2:1:1 3:1:1 Compound 22 tebuconazole pyraclostrobin 1:1:1 2:1:13:1:1 Compound 22 tebuconazole trifloxystrobin 1:1:1 2:1:1 3:1:1Compound 22 tebuconazole bixafen 1:1:2 2:1:2 3:1:2 Compound 22tebuconazole boscalid 1:1:2 2:1:2 3:1:2 Compound 22 tebuconazolecyflufenamid 1:2:1 2:2:1 3:2:1 Compound 22 tebuconazole fluopyram 1:1:22:1:2 3:1:2 Compound 22 tebuconazole isopyrazam 1:1:2 2:1:2 3:1:2Compound 22 tebuconazole metrafenone 1:1:2 2:1:2 3:1:2 Compound 22tebuconazole penthiopyrad 1:1:2 2:1:2 3:1:2 Compound 22 tebuconazoleproquinazid 1:1:1 2:1:1 3:1:1 Compound 22 tebuconazole quinoxyfen 1:1:12:1:1 3:1:1 Compound 22 tebuconazole sedaxane 1:1:2 2:1:2 3:1:2 Compound22 tebuconazole picoxystrobin proquinazid 1:1:1:1 2:1:1:1 3:1:1:1Compound 22 tebuconazole trifloxystrobin proquinazid 1:1:1:1 2:1:1:13:1:1:1 (*) Ratios of Component (a) relative to Component (b) insequence, by weight.

Tables C2 through C54 are each constructed the same as Table C1 aboveexcept that entries below the “Component (a)” column heading arereplaced with the respective Component (a) Column Entry shown below.Thus, for example, in Table C2 the entries below the “Component (a)”column heading all recite “Compound 18”, and the first line in below thecolumn headings in Table C2 specifically discloses a mixture of Compound18 with cyproconazole and azoxystrobin, and the illustrative weightratios of 1:1:1, 2:1:1 and 3:1:1 of Compound18:cyproconazole:azoxystrobin. Tables C3 through C54 are constructedsimilarly.

Table Number Component (a) Column Entries C2 Compound 18 C3 Compound 23C4 Compound 24 C5 Compound 36 C6 Compound 41 C7 Compound 45 C8 Compound87 C9 Compound 91 C10 Compound 118 C11 Compound 139 C12 Compound 148 C13Compound 172 C14 Compound 175 C15 Compound 193 C16 Compound 232 C17Compound 265 C18 Compound 266 C19 Compound 284 C20 Compound 286 C21Compound 287 C22 Compound 292 C23 Compound 297 C24 Compound 332 C25Compound 336 C26 Compound 343 C27 Compound 346 C28 Compound 349 C29Compound 351 C30 Compound 352 C31 Compound 357 C32 Compound 358 C33Compound 360 C34 Compound 361 C35 Compound 364 C36 Compound 365 C37Compound 367 C38 Compound 368 C39 Compound 369 C40 Compound 372 C41Compound 373 C42 Compound 374 C43 Compound 375 C44 Compound 376 C45Compound 377 C46 Compound 378 C47 Compound 379 C48 Compound 380 C49Compound 381 C50 Compound 382 C51 Compound 383 C52 Compound 384 C53Compound 385 C54 Compound 386

As mentioned in the Summary of the Invention, one aspect of the presentinvention is a composition comprising (i.e. a mixture or combination of)a compound of Formula 1, an N-oxide, or a salt thereof, and at least oneinvertebrate pest control compound or agent (e.g., insecticide,acaricide). Of note is a composition comprising component (a) and atleast one (i.e. one or more) invertebrate pest control compound oragent, which then can be subsequently combined with component (b) toprovide a composition comprising components (a) and (b) and the one ormore invertebrate pest control compounds or agents. Alternativelywithout first mixing with component (b), a biologically effective amountof the composition comprising component (a) with at least oneinvertebrate pest control agent can be applied to a plant or plant seed(directly or through the environment of the plant or plant seed) toprotect the plant or plant seed from diseases caused by fungal pathogensand injury caused by invertebrate pests.

For embodiments where one or more of invertebrate pest control compoundsare used, the weight ratio of these compounds (in total) to thecomponent (a) compounds is typically between about 1:3000 and about3000:1. Of note are weight ratios between about 1:300 and about 300:1(for example ratios between about 1:30 and about 30:1). One skilled inthe art can easily determine through simple experimentation thebiologically effective amounts of active ingredients necessary for thedesired spectrum of biological activity.

Of note is a composition of the present invention which comprises inaddition to a component (a) compound, alone or in combination withfungicidal component (b), at least one invertebrate pest controlcompound or agent selected from the group consisting of abamectin,acephate, acetamiprid, acetoprole, aldicarb, amidoflumet, amitraz,avermectin, azadirachtin, azinphos-methyl, bifenthrin, bifenazate,bistrifluron, buprofezin, carbofuran, cartap, chinomethionat,chlorfenapyr, chlorfluazuron, chlorantraniliprole, chlorpyrifos,chlorpyrifos-methyl, chlorobenzilate, chromafenozide, clothianidin,cyantraniliprole, cyflumetofen, cyfluthrin, beta-cyfluthrin,cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cyhexatin,cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon,dicofol, dieldrin, dienochlor, diflubenzuron, dimefluthrin, dimethoate,dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate,ethiprole, etoxazole, fenamiphos, fenazaquin, fenbutatin oxide,fenothiocarb, fenoxycarb, fenpropathrin, fenpyroximate, fenvalerate,fipronil, flonicamid, flubendiamide, flucythrinate, tau-fluvalinate,flufenerim, flufenoxuron, fonophos, halofenozide, hexaflumuron,hexythiazox, hydramethylnon, imicyafos, imidacloprid, indoxacarb,isofenphos, lufenuron, malathion, meperfluthrin, metaflumizone,metaldehyde, methamidophos, methidathion, methomyl, methoprene,methoxychlor, methoxyfenozide, metofluthrin, monocrotophos, nitenpyram,nithiazine, novaluron, noviflumuron, oxamyl, parathion,parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon,pirimicarb, profenofos, profluthrin, propargite, protrifenbute,pymetrozine, pyrafluprole, pyrethrin, pyridaben, pyridalyl,pyrifluquinazon, pyriprole, pyriproxyfen, rotenone, ryanodine,spinetoram, spinosad, spiridiclofen, spiromesifen, spirotetramat,sulfoxaflor, sulprofos, tebufenozide, tebufenpyrad, teflubenzuron,tefluthrin, terbufos, tetrachlorvinphos, tetramethylfluthin,thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tolfenpyrad,tralomethrin, triazamate, trichlorfon, triflumuron, Bacillusthuringiensis subsp. aizawai, Bacillus thuringiensis subsp. kurstaki,nucleopolyhedro viruses, encapsulated delta-endotoxins of Bacillusthuringiensis, baculoviruses, entomopathogenic bacteria,entomopathogenic viruses and entomopathogenic fungi.

In certain instances, combinations of a compound of Formula 1 or anN-oxide or salt thereof (i.e. component (a)), alone or in mixture withfungicidal component (b), with other biologically active (particularlyinvertebrate pest control) compounds or agents (i.e. active ingredients)can result in a greater-than-additive (i.e. synergistic) effect.Reducing the quantity of active ingredients released in the environmentwhile ensuring effective pest control is always desirable. Whensynergism of invertebrate pest control active ingredients occurs atapplication rates giving agronomically satisfactory levels ofinvertebrate pest control, such combinations can be advantageous forreducing crop production cost and decreasing environmental load.

Table D1 lists specific combinations of invertebrate pest control agentswith Compound 22 (identified in Index Table A) as a component (a)compound illustrative of mixtures and compositions comprising theseactive ingredients and methods using them according to the presentinvention. The second column of Table D1 lists the specific invertebratepest control agents (e.g., “Abamectin” in the first line). The thirdcolumn of Table D1 lists the mode of action (if known) or chemical classof the invertebrate pest control agents. The fourth column of Table D1lists embodiment(s) of ranges of weight ratios for rates at which theinvertebrate pest control agent is typically applied relative toCompound 22 alone or in combination with fungicidal component (b) (e.g.,“50:1 to 1:50” of abamectin relative to a Compound 22 by weight). Thus,for example, the first line of Table D1 specifically discloses thecombination of Compound 22 with abamectin is typically applied in aweight ratio between 50:1 to 1:50. The remaining lines of Table D1 areto be construed similarly

TABLE D1 Invertebrate Mode of Action Typical Component Pest Control orChemical Weight (a) Agent Class Ratio Compound 22 Abamectin macrocycliclactones   50:1 to 1:50 Compound 22 Acetamiprid neonicotinoids  150:1 to1:200 Compound 22 Amitraz octopamine receptor  200:1 to 1:100 ligandsCompound 22 Avermectin macrocyclic lactones   50:1 to 1:50 Compound 22Azadirachtin ecdysone agonists  100:1 to 1:120 Compound 22Beta-cyfluthrin sodium channel  150:1 to 1:200 modulators Compound 22Bifenthrin sodium channel  100:1 to 1:10 modulators Compound 22Buprofezin chitin synthesis  500:1 to 1:50 inhibitors Compound 22 Cartapnereistoxin analogs  100:1 to 1:200 Compound 22 Chloran- ryanodinereceptor  100:1 to 1:120 traniliprole ligands Compound 22 Chlorfenapyrmitochondrial electron  300:1 to 1:200 transport inhibitors   Compound22 Chlorpyrifos cholinesterase  500:1 to 1:200 inhibitors Compound 22Clothianidin neonicotinoids  100:1 to 1:400 Compound 22 Cyantrani-ryanodine receptor  100:1 to 1:120 liprole ligands Compound 22Cyfluthrin sodium channel  150:1 to 1:200 modulators Compound 22Cyhalothrin sodium channel  150:1 to 1:200 modulators Compound 22Cypermethrin sodium channel  150:1 to 1:200 modulators Compound 22Cyromazine chitin synthesis  400:1 to 1:50 inhibitors Compound 22Deltamethrin sodium channel   50:1 to 1:400 modulators Compound 22Dieldrin cyclodiene insecticides  200:1 to 1:100 Compound 22 Dinotefuranneonicotinoids  150:1 to 1:200 Compound 22 Diofenolan molting inhibitor 150:1 to 1:200 Compound 22 Emamectin macrocyclic lactones   50:1 to1:10 Compound 22 Endosulfan cyclodiene insecticides  200:1 to 1:100Compound 22 Esfenvalerate sodium channel  100:1 to 1:400 modulatorsCompound 22 Ethiprole GABA-regulated  200:1 to 1:100 chloride channelblockers Compound 22 Fenothiocarb  150:1 to 1:200 Compound 22 Fenoxycarbjuvenile hormone  500:1 to 1:100 mimics Compound 22 Fenvalerate sodiumchannel  150:1 to 1:200 modulators Compound 22 Fipronil GABA-regulated 150:1 to 1:100 chloride channel   blockers   Compound 22 Flonicamid 200:1 to 1:100 Compound 22 Flubendiamide ryanodine receptor  100:1 to1:120 ligands   Compound 22 Flufenoxuron chitin synthesis  200:1 to1:100 inhibitors   Compound 22 Hexaflumuron chitin synthesis  300:1 to1:50 inhibitors   Compound 22 Hydra- mitochondrial  150:1 to 1:250methylnon electron transport   inhibitors   Compound 22 Imidaclopridneonicotinoids 1000:1 to 1:1000   Compound 22 Indoxacarb sodium channel 200:1 to 1:50 modulators   Compound 22 Lambda- sodium channel   50:1 to1:250 cyhalothrin modulators Compound 22 Lufenuron chitin synthesis 500:1 to 1:250 inhibitors Compound 22 Meperfluthrin Sodium channel 100:1 to 1:400 modulators Compound 22 Metaflumizone  200:1 to 1:200Compound 22 Methomyl cholinesterase  500:1 to 1:100 inhibitors Compound22 Methoprene juvenile hormone  500:1 to 1:100 mimics Compound 22Methoxy- ecdysone agonists   50:1 to 1:50 fenozide Compound 22Nitenpyram neonicotinoids  150:1 to 1:200 Compound 22 Nithiazineneonicotinoids  150:1 to 1:200 Compound 22 Novaluron chitin synthesis 500:1 to 1:150 inhibitors Compound 22 Oxamyl cholinesterase  200:1 to1:200 inhibitors Compound 22 Pymetrozine  200:1 to 1:100 Compound 22Pyrethrin sodium channel  100:1 to 1:10 modulators Compound 22 Pyridabenmitochondrial  200:1 to 1:100 electron transport inhibitors Compound 22Pyridalyl  200:1 to 1:100 Compound 22 Pyriproxyfen juvenile hormone 500:1 to 1:100 mimics Compound 22 Ryanodine ryanodine receptor  100:1to 1:120 ligands Compound 22 Spinetoram macrocyclic lactones  150:1 to1:100 Compound 22 Spinosad macrocyclic lactones  500:1 to 1:10 Compound22 Spirodiclofen lipid biosynthesis  200:1 to 1:200 inhibitors Compound22 Spiromesifen lipid biosynthesis  200:1 to 1:200 inhibitors Compound22 Sulfoxaflor  200:1 to 1: 200 Compound 22 Tebufenozide ecdysoneagonists  500:1 to 1:250 Compound 22 Tetramethyl- Sodium channel  100:1to 1:400 fluthrin modulators Compound 22 Thiacloprid neonicotinoids 100:1 to 1:200 Compound 22 Thiamethoxam neonicotinoids 1250:1 to 1:1000Compound 22 Thiodicarb cholinesterase  500:1 to 1:400 inhibitorsCompound 22 Thiosultap-  150:1 to 1:100 sodium Compound 22 Tralomethrinsodium channel  150:1 to 1:200 modulators Compound 22 Triazamatecholinesterase  250:1 to 1:100 inhibitors Compound 22 Triflumuron chitinsynthesis  200:1 to 1:100 inhibitors Compound 22 Bacillus biologicalagents  50:1 to 1:10 thuringiensis Compound 22 Bacillus biologicalagents  50:1 to 1:10 thuringiensis delta-endotoxin Compound 22 NPV(e.g., biological agents  50:1 to 1:10 Gemstar)

Tables D2 through D54 are each constructed the same as Table D1 aboveexcept that entries below the “Component (a)” column heading arereplaced with the respective Component (a) Column Entry shown below.Thus, for example, in Table D2 the entries below the “Component (a)”column heading all recite “Compound 18”, and the first line in below thecolumn headings in Table D2 specifically discloses a mixture of Compound18 with abamectin. Tables D3 through D54 are constructed similarly.

Table Number Component (a) Column Entries D2 Compound 18 D3 Compound 23D4 Compound 24 D5 Compound 36 D6 Compound 41 D7 Compound 45 D8 Compound87 D9 Compound 91 D10 Compound 118 D11 Compound 139 D12 Compound 148 D13Compound 172 D14 Compound 175 D15 Compound 193 D16 Compound 232 D17Compound 265 D18 Compound 266 D19 Compound 284 D20 Compound 286 D21Compound 287 D22 Compound 292 D23 Compound 297 D24 Compound 332 D25Compound 336 D26 Compound 343 D27 Compound 346 D28 Compound 349 D29Compound 351 D30 Compound 352 D31 Compound 357 D32 Compound 358 D33Compound 360 D34 Compound 361 D35 Compound 364 D35 Compound 365 D37Compound 367 D38 Compound 368 D39 Compound 369 D40 Compound 372 D41Compound 373 D42 Compound 374 D43 Compound 375 D44 Compound 376 D45Compound 377 D46 Compound 378 D47 Compound 379 D48 Compound 380 D49Compound 381 D50 Compound 382 D51 Compound 383 D52 Compound 384 D53Compound 385 D54 Compound 386

One embodiment of invertebrate pest control agents (e.g., insecticidesand acaricides) for mixing with compounds of Formula 1 (and N-oxides andsalts thereof) include sodium channel modulators such as bifenthrin,cypermethrin, cyhalothrin, lambda-cyhalothrin, cyfluthrin,beta-cyfluthrin, deltamethrin, dimefluthrin, esfenvalerate, fenvalerate,indoxacarb, metofluthrin, profluthrin, pyrethrin and tralomethrin;cholinesterase inhibitors such as chlorpyrifos, methomyl, oxamyl,thiodicarb and triazamate; neonicotinoids such as acetamiprid,clothianidin, dinotefuran, imidacloprid, nitenpyram, nithiazine,thiacloprid and thiamethoxam; insecticidal macrocyclic lactones such asspinetoram, spinosad, abamectin, avermectin and emamectin; GABA(γ-aminobutyric acid)-regulated chloride channel blockers such asendosulfan, ethiprole and fipronil; chitin synthesis inhibitors such asbuprofezin, cyromazine, flufenoxuron, hexaflumuron, lufenuron,novaluron, noviflumuron and triflumuron; juvenile hormone mimics such asdiofenolan, fenoxycarb, methoprene and pyriproxyfen; octopamine receptorligands such as amitraz; ecdysone agonists such as azadirachtin,methoxyfenozide and tebufenozide; ryanodine receptor ligands such asryanodine, anthranilic diamides such as chlorantraniliprole,cyantraniliprole and flubendiamide; nereistoxin analogs such as cartap;mitochondrial electron transport inhibitors such as chlorfenapyr,hydramethylnon and pyridaben; lipid biosynthesis inhibitors such asspirodiclofen and spiromesifen; cyclodiene insecticides such asdieldrin; cyflumetofen; fenothiocarb; flonicamid; metaflumizone;pyrafluprole; pyridalyl; pyriprole; pymetrozine; spirotetramat; andthiosultap-sodium. One embodiment of biological agents for mixing withcompounds of component (a) include nucleopolyhedro virus such as HzNPVand AfNPV; Bacillus thuringiensis and encapsulated delta-endotoxins ofBacillus thuringiensis such as Cellcap, MPV and MPVII; as well asnaturally occurring and genetically modified viral insecticidesincluding members of the family Baculoviridae as well as entomophagousfungi. Of note is a composition comprising component (a) and at leastone additional biologically active compound or agent selected from theInvertebrate Pest Control Agents listed in Table D1 above.

The following TESTS demonstrate the control efficacy of compounds ofthis invention on specific pathogens. The pathogen control protectionafforded by the compounds is not limited, however, to these species. SeeIndex Table A for compound descriptions. The following abbreviations areused in the Index Tables which follow: Me is methyl, Ph is phenyl, OMeis methoxy, —CN is cyano, —NO₂ is nitro. Also, “pyridin-2-yl” issynonymous with “2-pyridinyl”, “pyridin-3-yl” is synonymous with“3-pyridinyl”, and “pyrimidin-5-yl” is synonymous with 5-pyrimidinyl”.The abbreviation “Ex.” stands for “Example” and is followed by a numberindicating in which example the compound is prepared. “Cmpd No.” meanscompound number. Mass spectra (M.S.) are reported as the molecularweight of the highest isotopic abundance parent ion (M+1) formed byaddition of H⁺ (molecular weight of 1) to the molecule, observed by massspectrometry using atmospheric pressure chemical ionization (AP⁺).

INDEX TABLE A

Cmpd No. R¹ R² Q¹ Q² X M.S 1 (Ex. 1) H Me 2,4-di-F—Ph 3-Cl—Ph NH ** 2 HMe 2,4-di-F—Ph 3,5-di-OMe—Ph NH 360 3 H Me 2,4-di-F—Ph 3-Cl—Ph NMe * 4 HMe 4-Cl—Ph 2,4-di-F—Ph NH 334 5 H Me 4-Cl—Ph 3,5-di-F—Ph NH 334 6 H Me4-Cl—Ph 3,5-di-F—Ph NMe 348 7 H Me 2-Cl-4-F—Ph 3-Cl-4-F—Ph NH 369 8 H Me2-Cl-4-F—Ph 3-F—Ph NH 334 9 H Me 2-Cl-4-F—Ph 3,5-di-F—Ph NH 352 10 H Me4-Cl—Ph 2,3,5-tri-F—Ph NH 352 11 H Me 2-Cl-4-F—Ph 4-F—Ph NH 334 12 H Me2-Cl-4-F—Ph 2-F—Ph NH 334 13 H Me 2-Cl-4-F—Ph 2,4-di-F—Ph NH 352 14 H Me2,4,6-tri-F—Ph 3-F-4-Cl—Ph NH 370 15 H Me 2-F-4-OMe—Ph 4-Cl—Ph O 347 16H Me 3,5-di-OMe—Ph 4-Cl—Ph O 359 17 (Ex. 2) H Me 2-Cl-4-F—Ph2,6-di-F-4-OMe—Ph NH ** 18 H Me 2-Cl-4-F—Ph 2,4,6-tri-F—Ph NH 370 19 HMe 2-Cl-4-F—Ph 4-Cl—Ph NH 350 20 H Me 2-Cl-4-F—Ph 2-F-4-NO₂—Ph O 380 21H Me 2-Cl-4-F—Ph 2-F-4-OMe—Ph O 365 22 H Me 2,6-di-F-4-OMe—Ph 4-Cl—Ph NH364 23 H Me 2,6-di-F-4-OMe—Ph 2,4-di-F—Ph NH 366 24 (Ex. 3) H Me2,6-di-F-4-OMe—Ph 2,4,6-tri-F—Ph NH ** 25 H Me 3-Cl—Ph 2,6-di-F-4-OMe—PhNH 364 26 H Me 2,4,6-tri-F—Ph 4-NO₂—Ph O 364 27 H Me 2,4,6-tri-F—Ph4-Cl—Ph O 353 28 H Me 4-Cl—Ph 2,4,6-tri-F—Ph NH 352 29 H Me 4-Cl—Ph2,6-di-F-4-OMe—Ph NH 364 30 H Me 2,4,6-tri-F—Ph 2,6-di-Cl-4-CF₃—Ph O 45531 H Me 2,4,6-tri-F—Ph 2,6-di-F-4-CN—Ph O 380 32 H Me 2,4,6-tri-F—Ph2-Cl-4-NO₂—Ph O 398 33 H Me 4-Cl—Ph 2,6-di-F—Ph NH 334 34 H Me2,6-di-F-4-OMe—Ph 6-Cl-pyridin-3-yl NH 365 35 H Me 3,4-di-F—Ph2,4,6-tri-F—Ph NH 354 36 H Me 3,4-di-F—Ph 2,6-di-F-4-OMe—Ph NH 366 37 HMe 2,6-di-F—Ph 3,5-di-OMe—Ph NH 360 38 H Me 2,4,6-tri-F—Ph 2,4-di-Cl—PhO 387 39 H Me 2,4,6-tri-F—Ph 5-Cl-pyridin-2-yl O 354 40 H Me2,6-di-F-4-OMe—Ph 2,4-di-Cl—Ph O 399 41 H Me 2,4-di-F—Ph 2,4,6-tri-F—PhNH 354 42 H Me 2,4-di-F—Ph 2,6-di-F-4-OMe—Ph NH 366 43 H Me 3-F—Ph2,6-di-F-4-CN—Ph O 344 44 H Me 4-Cl—Ph 2,6-di-F-4-CN—Ph O 360 45 (Ex. 4)H Me 2-Cl-4-F—Ph 2,6-di-F-4-CN—Ph O ** 46 H Me 2-F-4-OMe—Ph2,6-di-F-4-CN—Ph O 374 47 H Me 2,6-di-F-4-OMe—Ph 5-Cl-pyridin-2-yl O 36648 H Me 2,6-di-F-4-OMe—Ph 3,4-di-F—Ph NH 366 49 H Me 2,6-di-F-4-OMe—Ph3-F-4-Cl—Ph NH 382 50 H Me 2,6-di-F-4-OMe—Ph 4-Me—Ph NH 344 51 H Me2,6-di-F-4-OMe—Ph 2,4-di-OMe—Ph NH 390 52 H Me 4-Me—Ph 2-Cl-4-NO₂—Ph O358 53 Ph Me 2,4,6-tri-F—Ph 2,6-di-F-4-NO₂—Ph O 476 54 (Ex. 8) H Me2,4,6-tri-F—Ph 2,6-di-F-4-NO₂—Ph O ** 55 H Me 4-Me—Ph 2-Cl-4-OMe—Ph O343 56 H Me 4-Cl—Ph 4-OMe—Ph NH 328 57 H Me 2,4-di-Cl—Ph 2,4-di-OMe—PhNH 392 58 (Ex. 10) H Me 2,6-di-F-4-OMe—Ph 2,6-di-F-4-Cl—Ph O ** 59 H Me2,6-di-F-4-OMe—Ph 2,4-di-OMe-6-Cl—Ph NH 424 60 H Me 4-Cl—Ph2-Cl-4-OMe—Ph NH 362 61 Me Me 4-Cl—Ph 2,6-di-F—Ph NH 348 62 H Me2,4-di-Cl—Ph 2,6-di-F-4-OMe—Ph NH 398 63 Me Me 2,6-di-F—Ph 3,5-di-OMe—PhNH 374 64 H Me 2,4,6-tri-F—Ph 3,5-di-Cl-pyridin-2-yl O 388 65 —CO₂Et Me2,4,6-tri-F—Ph 2,6-di-F, 4-NO₂—Ph O 472 66 H Me 2,6-di-F-4-OMe—Ph5-Me-pyridin-2-yl NH 345 67 H Me 2-Cl-4-F—Ph 5-CN-pyridin-2-yl NH 342 68—CO₂H Me 2,4,6-tri-F—Ph 2,6-di-F-4-NO₂—Ph O 444 69 (Ex. 5) H Me2,4-di-Cl—Ph 2,4-di-F—Ph NH ** 70 Me Me 2,4-di-Cl—Ph 2,4-di-F—Ph NH 38271 H Me 2-Cl-4-F—Ph 2-F-4-(NHC(O)Me)—Ph O 392 72 H Me 2,4-di-F—Ph3,4-di-OMe—Ph NH 360 73 H Me 2-Cl-4-F—Ph 3,5-di-Cl-pyridin-2-yl NH 38774 H Me 2,4-di-Cl—Ph 3,4-di-OMe—Ph NH 392 75 H Me 2,4-di-Cl—Ph2,4,6-tri-F—Ph NH 386 76 H Me 2,4-di-F—Ph 6-Cl-pyridin-3-yl NH 331 77 HMe 2,6-di-F-4-OMe—Ph 2,6-di-F-4-NH₂—Ph O 382 78 H Me 2,4,6-tri-F—Ph2,6-di-F-4-OMe—Ph NH 384 79 H Me 4-Me—Ph 2,4,6-tri-F—Ph NH 332 80 H Me4-Me—Ph 2,6-di-F-4-OMe—Ph NH 344 81 H Me 2,6-di-F-4-OMe—Ph5-Cl-2,4-di-OMe—Ph NH 424 82 H Me 2,6-di-F-4-OMe—Ph 2,6-di-F-4-CN—Ph NH391 83 H Me 2,6-di-F-4-OMe—Ph 2,6-di-F-4-OMe—Ph NH 396 84 H Me2,6-di-F-4-OMe—Ph 2,6-di-F—Ph O 367 85 H Me 3,5-di-OMe—Ph2,6-di-F-4-CN—Ph O 386 86 H Me 6-Cl-pyridin-3-yl 2,6-di-F-4-CN—Ph O 36187 H Me 2,6-di-F-4-OMe—Ph 2-Cl-4-F—Ph NH 382 88 H Me 2,6-di-F-4-OMe—Ph4-F-2-Me—Ph NH 362 89 H Me 4-F-2-OMe—Ph 2,6-di-F-4-CN—Ph O 374 90 H Me2,6-di-F-4-OMe—Ph 4-Br-2,6-di-F—Ph O 447 91 H Me 2-Cl-4-F—Ph2,6-di-F-4-CN—Ph NH 377 92 H Me 2,4,6-tri-F—Ph 2,6-di-F-4-CN—Ph NH 37993 H Me 2,4,6-tri-F—Ph 3,4-di-OMe—Ph NH 378 94 H Me 2,4,6-tri-F—Ph6-OMe-pyridin-3-yl NH 349 95 H Me 2,6-di-F-4-OMe—Ph 6-OMe-pyridin-3-ylNH 361 96 H Me 2,4,6-tri-F—Ph 2-F-4-CN—Ph O 362 97 H Me 4-F-2-Me—Ph2,6-di-F-4-CN—Ph O 358 98 H Me 2,4,6-tri-F—Ph 2-Cl-4-CN—Ph O 378 99 H Me2,4,6-tri-F—Ph 2,5-di-F-4-CN—Ph O 380 100 H Me 2,4,6-tri-F—Ph5-Cl-2,4-di-OMe—Ph NH 412 101 H Me 2,4,6-tri-F—Ph 3,5-di-Cl-pyridin-2-ylNH 386 102 H Me 2,6-di-F-4-OMe—Ph 3,5-di-Cl-pyridin-2-yl NH 398 103 H Me2,6-di-F-4-OH—Ph 2,4-di-F—Ph NH 352 104 H Me 2-Cl-4-OMe—Ph2,4,6-tri-F—Ph NH 382 105 H Me 2,6-di-F-4-OS(O)₂CF₃ 2,4-di-F—Ph NH 484106 H Me 2,6-di-F-4-CN—Ph 2,4-di-F—Ph NH 361 107 H Me 2-Cl-4-F—Ph2,6-di-Cl-pyridin-3-yl NH 386 108 H c-Pr 2-Cl-4-F—Ph 2,4-di-F—Ph NH 378109 H Me 2,4,6-tri-F—Ph 3,5-di-F-pyridin-2-yl NH 355 110 H Me2,6-di-F-4-CN—Ph 4-Cl—Ph NH *** 111 H Me 2,6-di-F-4-CN—Ph 4-F—Ph NH ***112 H Me 2,6-di-F-4-CN—Ph 2-Cl-4-F—Ph NH *** 113 H Me 2,6-di-F-4-CN—Ph3-F-4-OMe—Ph NH *** 114 H Me 2,6-di-F-4-CN—Ph 3,4-di-F—Ph NH *** 115 HMe 2,6-di-F-4-CN—Ph 3-Cl—Ph NH *** 116 H Me 2-Cl-4-F—Ph 3-F-5-CN—Ph O360 117 H Me 2,6-di-F-4-OMe—Ph 2-Cl-4-CN—Ph NH 389 118 H Me 2-Cl-4-F—Ph2-F-4-CN—Ph O 360 119 H Me 2-Cl-4-F—Ph 2-Cl-4-NO₂—Ph O 396 120 H Me2,4,6-tri-F—Ph 2-F-4-CN—Ph NH 361 121 H Me 2-Cl-4-F—Ph 2,6-di-F-4-NO₂—PhO 398 122 H Me 2-Cl-4-F—Ph 4-F-2-NO₂—Ph O 380 123 H Me 2,6-di-F-4-CN—Ph3,4-di-Cl—Ph NH *** 124 H Me 2,6-di-F-4-CN—Ph 4-Me—Ph NH *** 125 H Me2,6-di-F-4-CN—Ph 4-Cl-3-F—Ph NH *** 126 H Me 2,6-di-F-4-CN—Ph 4-OMe—PhNH *** 127 H Me 2,6-di-F-4-CN—Ph 4-F-3-OMe—Ph NH 373 128 H Me2,6-di-F-4-OMe—Ph 3,5-di-F-pyridin-2-yl NH 367 129 H Me 2,4,6-tri-F—Ph4-Cl-3-F—Ph O *** 130 H Me 2,4,6-tri-F—Ph 4-Br-3-F—Ph O *** 131 H Me2,4,6-tri-F—Ph 3-F-4-NO₂—Ph O *** 132 H Me 2-Cl-4-F—Ph 3,4,5-tri-F—Ph NH370 133 H Me 2,6-di-F-4-CN—Ph 2,4,6-tri-F—Ph NH *** 134 H Me2,6-di-F-4-CN—Ph 2,6-di-F-4-OMe—Ph NH *** 135 H Me 2,4,6-tri-F—Ph3-Me-4-NO₂—Ph O *** 136 H Me 2,6-di-F-4-CN—Ph 3-F—Ph NH *** 137 H Me2,6-di-F-4-CN—Ph 2,5-di-F—Ph NH *** 138 H Me 2,6-di-F-4-CN—Ph2,4,5-tri-F—Ph NH *** 139 H Me 2-Cl-4-F—Ph 2-Cl-4-CN—Ph O 376 140 H Me2,6-di-F-4-OMe—Ph 2,6-di-F-4-CN—Ph O 392 141 H Me 2,6-di-F-4-OEt—Ph2,4-di-F—Ph NH 380 142 H Me 2,6-di-F-4-CN—Ph 5-Cl-2-F—Ph NH *** 143 H Me2,6-di-F-4-CN—Ph 4-Cl-2-F—Ph NH *** 144 H Me 2,6-di-F-4-CN—Ph3-Cl-4-F—Ph NH *** 145 H Me 2,6-di-F-4-CN—Ph 2,3-di-F—Ph NH *** 146 H Me2,6-di-F-4-CN—Ph 2,5-di-Cl—Ph NH *** 147 H Me 2,6-di-F-4-CN—Ph2,3-di-Cl—Ph NH *** 148 H Me 2-Cl-4-F—Ph 2,5-di-F-4-CN—Ph O 378 149 H Me2-Cl-4-F—Ph 4-F-2-CN—Ph O 360 150 H Me 2-Cl-4-F—Ph 2-Cl-4,5-di-CN—Ph O401 151 H Me 2,4,6-tri-F—Ph 3-OMe-4-NO₂—Ph O *** 152 H Me2,6-di-F-4-OMe—Ph 4-Cl-3-F—Ph O 383 153 H Me 2,6-di-F-4-OMe—Ph4-Br-3-F—Ph O 429 154 H Me 2-Cl-4-F—Ph 3,5-di-F-pyridin-2-yl NH 353 155H Me 2-Cl-4-OMe—Ph 2,6-di-F-4-CN—Ph O 390 156 H Me 2,4,6-tri-F—Ph3-CN-4-NO₂—Ph O *** 157 H Me 2,4,6-tri-F—Ph 4-Cl-3-Me—Ph O *** 158 H Me2-Cl-4-F—Ph 2,6-di-F-4-OMe—Ph NEt 410 159 H Me 2-Cl-4-F—Ph2,6-di-F-4-OMe—Ph NCH₂CH═CH₂ 422 160 H Me 2-Cl-4-OMe—Ph 2,4-di-F—Ph NH364 161 H Me 2-Cl-4-OMe—Ph 2,6-di-F—Ph NH 364 162 H Me 2-Cl-4-F—Ph2-Cl-4-CN—Ph NH 375 163 H Me 2,4,6-tri-F—Ph 2-Cl-4,5-di-CN—Ph O 403 164H Me 2,4,6-tri-F—Ph 4-Cl-3-OMe—Ph O *** 165 H Me 2,4,6-tri-F—Ph4-Br-3-Me—Ph O *** 166 H Me 2,4,6-tri-F—Ph 4-Br-3-OMe—Ph O 429 167 H Me2,4,6-tri-F—Ph 2,3,5-tri-F—Ph O 373 168 H Me 2-Cl-4-F—Ph 3,4-di-CN—Ph O367 169 H Me 2,4,6-tri-F—Ph 3,4-di-CN—Ph O 369 170 H Me 2,4-di-F—Ph2,6-di-F-4-CN—Ph O 362 171 H Me 2-Cl-4-F—Ph 2,3,6-tri-F—Ph NH 370 172 HMe 2-Cl-4-F—Ph 2,6-di-F—Ph NH 352 173 H Me 2-Cl-4-F—Ph 2,5-di-F—Ph NH352 174 H Me 2-Cl-4-OMe—Ph 2,3,6-tri-F—Ph NH 382 175 H Me 2-Cl-4-F—Ph2-Cl-4-F—Ph NH 368 176 H Me 2-Cl-4-OMe—Ph 2,5-di-F—Ph NH 364 177 H Me2-Cl-6-F—Ph 2,4-di-F—Ph NH 352 178 H Me 2,6-di-F—Ph 2,4-di-F—Ph NH ***179 H Me 2,6-di-F—Ph 2,4-di-Cl—Ph NH *** 180 H Me 2,6-di-F—Ph2-F-4-OMe—Ph NH *** 181 H Me 2-F—Ph 2,4-di-F—Ph NH 318 182 H Me 2-F—Ph2,4,6-tri-F—Ph NH 336 183 H Me 2-F—Ph 2,6-di-F-4-OMe—Ph NH 348 184 H Me2-F—Ph 4-F—Ph NH 300 185 H Me 2,6-di-F-4-OMe—Ph 4-Cl-3-Me—Ph O 379 186 HMe 2,6-di-F-4-OMe—Ph 4-Br-3-Me—Ph O *** 187 H Me 2,4,6-tri-F—Ph3-F-4-Me—Ph O *** 188 H Me 2,6-di-F-4-OMe—Ph 3-F-4-Me_Ph O 363 189 H Me2-Cl-4-F—Ph 3,5-di-F-pyridin-2-yl O 354 190 H Me 2-Cl-6-F—Ph2,6-di-F-4-OMe—Ph NH 382 191 H Me 2-Cl-6-F—Ph 2,4,6-tri-F—Ph NH 369 192H Me 2-Cl-6-F—Ph 2,6-di-F-4-CN—Ph NH 377 193 H Me 2-Cl-6-F—Ph2-Cl-4-F—Ph NH 368 194 H Me 2,4-di-F—Ph 4-F—Ph NH *** 195 H Me2,4-di-F—Ph 4-Cl—Ph NH *** 196 H Me 2,6-di-F—Ph 2-F-4-CN—Ph NH 343 197 HMe 2,6-di-F—Ph 2,5-di-F—Ph NH *** 198 H Me 2,6-di-F—Ph 2,3-di-F—Ph NH*** 199 H Me 2,6-di-F—Ph 4-F-2-OMe—Ph NH *** 200 H Me 2,6-di-F—Ph3-OMe—Ph NH *** 201 H Me 2,6-di-F—Ph 2-Cl-4-OMe—Ph NH *** 202 H Me2,3-di-F—Ph 2,4-di-F—Ph NH 336 203 H Me 2,3-di-F—Ph 2,4,6-tri-F—Ph NH354 204 H Me 2,3-di-F—Ph 2,6-di-F-4-OMe—Ph NH 366 205 H Me 2,3-di-F—Ph4-F—Ph NH 318 206 H Me 2,6-di-F-4-OMe—Ph 4-Cl—Ph O 365 207 H Me2,4-di-F—Ph 2-Cl-4-F—Ph NH *** 208 H Me 2,6-di-F-4-OMe—Ph 2,4-di-F—PhCHOH 381 209 H Me 2,4,6-tri-F—Ph 3,4-di-Me—Ph O *** 210 H Me2,6-di-F-4-OMe—Ph 3,4-di-Me—Ph O *** 211 H Me 2,6-di-F-4-OMe—Ph4-Cl-3-OMe—Ph O *** 212 H Me 2,6-di-F-4-OMe—Ph 4-Br-3-OMe—Ph O *** 213 HMe 2,4,6-tri-F—Ph 3-OMe—Ph O 349 214 H Me 2,4-di-F—Ph 2,3-di-F—Ph NH ***215 H Me 2,6-di-F—Ph 2-Cl-5-OMe—Ph NH *** 216 H Me 2,6-di-F—Ph2-F-5-OMe—Ph NH *** 217 H Me 2,4,6-tri-F—Ph 3-OMe-4-Me—Ph O *** 218 H Me2,6-di-F-4-OMe—Ph 4-Cl-3-CN—Ph O *** 219 H Me 2,4,6-tri-F—Ph 3-Me—Ph O333 220 H Me 2,6-di-F-4-OMe—Ph 3-Me—Ph O 345 221 H Me 2,6-di-F-4-OMe—Ph3-OMe—Ph O 361 222 H Me 2,4,6-tri-F—Ph 3-CN—Ph O 344 223 H Me2,6-di-F-4-OMe—Ph 3-CN—Ph O 356 224 H Me 2,4,6-tri-F—Ph 4-Cl-3-CN—Ph O*** 225 H Me 2,4,6-tri-F—Ph 4-Br-3-CN—Ph O *** 226 H Me 2,4-di-F—Ph2,5-di-F—Ph NH *** 227 H Me 2,4-di-F—Ph 2-Cl-5-OMe—Ph NH *** 228 H Me2,4-di-F—Ph 2-F-4-OMe—Ph NH *** 229 H Me 2,4-di-F—Ph 2,4,5-tri-F—Ph NH*** 230 H Me 2,4-di-F—Ph 2,4-di-F—Ph NH 336 231 H Me 2,4-di-F—Ph2,3-di-Cl—Ph NH *** 232 H Me 2-Br-4-F—Ph 2,6-di-F-4-CN—Ph O 423 233 H Me2-Br-4-F—Ph 2,5-di-F-4-CN—Ph O 423 234 H Me 2-Cl-4-F—Ph 4-F-3-CN—Ph NH359 235 H Me 2-Cl-4-F—Ph 2-Cl-5-CN—Ph NH 375 236 H Me 2-CF₃—Ph2-Cl-4-F—Ph NH 384 237 H Me 2-CF₃—Ph 4-F—Ph NH 350 238 H Me 2-CF₃—Ph2,4-di-F—Ph NH 368 239 H Me 2-CF₃—Ph 2,4,6-tri-F—Ph NH 386 240 H Me2-CF₃—Ph 2,6-di-F-4-OMe—Ph NH 398 241 H Me 2,4,6-tri-F—Ph3-Cl-pyridin-2-yl NH 353 242 H Me 2,4-di-F—Ph 2-Cl-4-OMe—Ph NH *** 243 HMe 2,4-di-F—Ph 2,4-di-Cl—Ph NH *** 244 H Me 2,4-di-F—Ph 2-F-5-OMe—Ph NH*** 245 H Me 2,4-di-F—Ph 2,5-di-Cl—Ph NH *** 246 H Me 2,4-di-F—Ph2-F-4-CN—Ph NH *** 247 H Me 2,6-di-F—Ph 2,6-di-F—Ph NH *** 248 H Me2-Br—Ph 2,4,6-tri-F—Ph NH 398 249 H Me 2,6-di-F-4-OMe—Ph 3-OMe-4-Me—Ph O*** 250 H Me 2,4,6-tri-F—Ph 3-CN-4-Me—Ph O *** 251 H Me 2-CF₃—Ph3,5-di-Cl-pyridin-2-yl NH 401 252 H Me 2-Cl-6-F—Ph3,5-di-Cl-pyridin-2-yl NH 387 253 H Me 2-F-6-CF₃—Ph 2-Cl-4-F—Ph NH 402254 H Me 2-F-6-CF₃—Ph 4-F—Ph NH 368 255 H Me 2-F-6-CF₃—Ph 2,4-di-F—Ph NH368 256 H Me 2,4-di-F—Ph 2,6-di-F—Ph NH *** 257 H Me 2,6-di-F—Ph2,6-di-F-4-OMe—Ph NH *** 258 H Me 2,6-di-F-4-OMe—Ph 4-Br-3-CN—Ph O ***259 H Me 2,6-di-F-4-OMe—Ph 3-CN-4-Me—Ph O *** 260 H Me 2-Br-4-F—Ph3-F-5-CF₃-pyridin-2-yl O 449 261 H Me 2-Br-4-F—Ph3-Cl-5-CF₃-pyridin-2-yl O 465 262 H Me 2-F-6-CF₃—Ph 2,4,6-tri-F—Ph NH404 263 H Me 2-F-6-CF₃—Ph 2,6-di-F-4-OMe—Ph NH 416 264 H Me 2-F-6-CF₃—Ph3,5-di-F-pyridin-2-yl NH 387 265 H Me 2-Cl-4-F—Ph 2-Br-4-F—Ph NH 413 266H Me 2-Br-4-F—Ph 2,4,6-tri-F—Ph NH 415 267 H Me 2-Cl-4-OMe—Ph3,5-di-Cl-pyridin-2-yl NH 399 268 H Me 2-Cl-4-F—Ph 2-Cl-pyrimidin-5-ylNH *** 269 H Me 2-Cl-4-F—Ph 2-Me-pyrimidin-5-yl NH *** 270 H Me2-Cl-4-F—Ph pyrimidin-5-yl NH *** 271 H Me 2-Cl—Ph 2,6-di-F-4-CN—Ph O*** 272 H Me 2-Br—Ph 2,6-di-F-4-CN—Ph O *** 273 H Me 2,3-di-Cl—Ph2,6-di-F-4-CN—Ph O *** 274 H Me 2,3-di-F—Ph 2,6-di-F-4-CN—Ph O *** 275 HMe 2,5-di-Cl—Ph 2,6-di-F-4-CN—Ph O *** 276 H Me 2-Cl-5-F—Ph2,6-di-F-4-CN—Ph O *** 277 H Me 2-Cl-5-OMe—Ph 2,6-di-F-4-CN—Ph O *** 278H Me 2-F-5-OMe—Ph 2,6-di-F-4-CN—Ph O *** 279 H Me 2-Cl-6-F—Ph3,5-di-F-pyridin-2-yl NH 353 280 H Me 2-CF₃—Ph 3,5-di-F-pyridin-2-yl NH369 281 H Me 2,4-di-F—Ph 2-Cl-3-OMe—Ph NH *** 282 H Me 2-Cl-4-OMe—Ph2,4-di-Cl—Ph NH 397 283 H Me 2-Cl-6-F—Ph 2,4-di-Cl—Ph NH 386 284 H Me2-Br-4-F—Ph 2-F-4-CN—Ph O 406 285 H Me 2-Br-4-F—Ph 2-Cl-4-CN—Ph O 422286 H Me 2-Cl-4-F—Ph 4-Cl-2,6-di-F—Ph NH 386 287 H Me 2-Cl-4-F—Ph2-Cl-4,6-di-F—Ph NH 386 288 H Me 2-Cl-4-F—Ph 4-OMe—Ph NH 346 289 H Me2,6-di-F—Ph 2-Cl-3-OMe—Ph NH *** 290 H Me 2,4-di-F—Ph 2,6-di-F-4-CN—PhNH *** 291 H Me 2,4-di-F—Ph 2-Cl-5-CN—Ph NH *** 292 H Me 2-Br-4-F—Ph2-Cl-4,6-di-F—Ph NH 431 293 H Me 2-Cl-4-F—Ph 2,4,6-tri-F—Ph NMe *** 294H Me 2-Cl-4-F—Ph 2,4,6-tri-F—Ph NEt *** 295 H Me 2-Br-4-F—Ph3,5-di-Cl-pyridin-2-yl NH 430 296 H Me 2-Cl-4-F—Ph 2,6-di-Cl-4-OMe—Ph NH413 297 H Me 2,6-di-F—Ph 2-Cl-4,6-di-F—Ph NH 370 298 H Me 2-Cl-6-F—Ph2-Cl-4,6-di-F—Ph NH 386 299 H Me 2-Cl-4-F—Ph 2,4-di-Cl—Ph NH 383 300 HMe 2,6-di-F—Ph 2,4,6-tri-F—Ph NH *** 301 H Me 2,6-di-F—Ph2,6-di-F-4-CN—Ph NH *** 302 H Me 2,3-di-Cl—Ph 2,4-di-F—Ph NH 368 303 HMe 2,3-di-Cl—Ph 3,5-di-Cl-pyridin-2-yl NH 400 304 H Me 2-Cl-4-F—Ph2,4,6-tri-F—Ph NS(O)₂Me *** 305 H Me 2-F—Ph 2,6-di-F-4-CN—Ph O *** 306 HMe 2-CF₃—Ph 2,6-di-F-4-CN—Ph O *** 307 H Me 2-Cl-5-CF₃—Ph2,6-di-F-4-CN—Ph O *** 308 H Me 2-Cl-pyridin-3-yl 2,6-di-F-4-CN—Ph O ***309 H Me 2-Cl-4-F—Ph 2,4,6-tri-F—Ph NCH₂OMe *** 310 H Me 2-Cl-4-OMe—Ph2-F-4-CN—Ph O 372 311 H Me 2-Cl-4-OMe—Ph 2-Cl-4-CN—Ph O 388 312 H Me2-Br-4-F—Ph 2,4-di-F—Ph NH 398 313 H Me 2-Br-4-F—Ph 2-Br-4-F—Ph NH 458314 H Me 2-Br-4-F—Ph 2-Cl-4-F—Ph NH 414 315 H Me 2-Cl—Ph 2,4-di-F—Ph NH334 316 H Me 2-Br-4-F—Ph 2,6-di-Cl-4-F—Ph NH 448 317 H Me 2-Br-4-F—Ph4-OMe—Ph NH 392 318 H Me 2-Br-4-OMe—Ph 2-Cl-4-CN—Ph O 433 319 H Me2-Br-4-OMe—Ph 2-F-4-CN—Ph O 418 320 H Me 2-Cl—Ph 3,5-di-Cl-pyridin-2-ylNH 368 321 H Me 2,6-di-F—Ph 3,5-di-Cl-pyridin-2-yl NH 369 322 H Me2-Cl-4-F—Ph 2-Cl-4-OMe—Ph NH 380 323 H Me 2-Br-4-F—Ph 2,6-di-Cl-4-OMe—PhNH 459 324 H Me 2-Br-4-F—Ph 2-Cl-4-OMe—Ph NH 425 325 H Me 2-Cl-4-F—Ph2-Cl-4-OEt—Ph NH 394 326 H Me 2-Cl-4-F—Ph 2,4,6-tri-F—Ph NCH₂CN 409 327H Me 2,6-di-Cl—Ph 2,4-di-Cl—Ph NH *** 328 H Me 2,4-di-F—Ph3,5-di-Cl-pyridin-2-yl NH 369 329 H Me 2,5-di-F—Ph 2,6-di-F-4-CN—Ph O*** 330 H Me 2-Cl-4,6-di-F—Ph 2,6-di-F-4-CN—Ph NH 395 331 H Me2-Cl-4-CN—Ph 2,4-di-F—Ph NH 359 332 H Me 2-Cl-4-CN—Ph 2-Cl-4,6-di-F—PhNH 393 333 H Me 2,6-di-Cl—Ph 4-OMe—Ph NH *** 334 H Me 2,6-di-Cl—Ph2-Cl-4-F—Ph NH *** 335 H Me 2-Cl-4-CN—Ph 2,6-di-F—Ph NH 359 336 H Me2-Cl-4-CN—Ph 4-Cl-2,6-di-F—Ph NH 393 337 H Me 2,6-di-Cl—Ph 4-F—Ph NH ***338 H Me 2-Cl-4-CN—Ph 2-Cl-4-F—Ph NH 375 339 H Me 2,6-di-Cl—Ph2,4-di-F—Ph NH *** 340 H Me 2,6-di-Cl—Ph 2-Br-4-F—Ph NH *** 341 H Me2,6-di-Cl—Ph 2,6-di-Cl-4-F—Ph NH *** 342 H Me 2-Cl-6-F—Ph 2-F-4-CN—Ph O360 343 H Me 2,4-di-F—Ph 2-Cl-4,6-di-F—Ph NH 369 344 H Me 2-Cl-4-F—Ph2-F-4-NO₂—Ph NH 380 345 H Me 2-Cl-4-F—Ph 2-F-5-NO₂—Ph NH 380 346 H Me2,4-di-F—Ph 2-Br-4-F—Ph NH 398 347 H Me 4-Cl-2-F—Ph 2-F-4-CN—Ph O 360348 H Me 2,4-di-F—Ph 2-Br-6-Cl-4-F—Ph NH 432 349 H Me 2,6-di-F—Ph4-Cl-2,6-di-F—Ph NH 370 350 H Me 2-Cl-4-F—Ph 4-F—Ph CHOH 349 351 (Ex. 6)H Me 2-Cl-4-F—Ph 2,4-di-F—Ph CHOH ** 352 H Me 2-Cl-4-F—Ph 2-Cl-4-F—PhCHOH 383 353 H Me 2,4-di-Cl—Ph 2,6-di-F—Ph NH *** 354 H Me 2,4-di-Cl—Ph2-Cl-4-F Ph NH *** 355 H Me 2,4-di-Cl—Ph 4-OMe—Ph NH *** 356 H Me2-Cl-4-F—Ph 2,3,6-tri-F—Ph CHOH 385 357 H Me 2,4-di-F—Ph4-Cl-2,6-di-F—Ph NH 370 358 H Me 2,6-di-F—Ph 2-Cl-4-CN—Ph O 360 359 H Me2,4-di-F—Ph 2-F-4-CN—Ph O 376 360 H Me 2-Br-4-F—Ph 4-Cl-2,6-di-F—Ph NH432 361 H Me 2,6-di-F—Ph 2-F-4-CN—Ph O 344 362 H Me 2,4-di-Cl—Ph2-Cl-4-CN—Ph O 394 363 H Me 2,4-di-Cl—Ph 2,6-di-Cl-4-F—Ph NH *** 364 HMe 2,4-di-F—Ph 4-Br-2,6-di-F—Ph NH 416 365 H Me 2-Cl-4-F—Ph4-Br-2,6-di-F—Ph NH 432 366 H Me 2-Cl-4-F—Ph 4-Br-2-F—Ph NH 414 367 H Me2-Cl-4-F—Ph 2,4-di-Cl-6-F—Ph NH 402 368 H Me 2,4-di-F—Ph2,6-di-Cl-4-F—Ph NH 369 H Me 2-Cl-4-F—Ph 2,6-di-Cl-4-F—Ph NH 370 (Ex. 7)H Me 2-Cl-4-F—Ph 2,4-di-F—Ph C(═O) ** 371 (Ex. 9) H Me 2,4,6-tri-F—Ph2,6-di-F-4-NH₂—Ph O ** 372 H Me 2,4-di-F—Ph 2-Br-4-CN—Ph O 373 H Me2,4-di-F—Ph 2-Cl-4-CN—Ph O 374 H Me 2,4-di-F—Ph 2,4-di-Cl-6-F—Ph NH 386375 H Me 2,6-di-F—Ph 2,6-di-Cl-4-F—Ph NH 376 H Me 2,4-di-F—Ph2-Br-4,6-di-F—Ph NH 416 377 H Me 2-Cl-4-F—Ph 2-Br-4,6-di-F—Ph NH 432 378H Me 2,6-di-F—Ph 4-Br-2,6-di-F—Ph NH 379 H Me 2,6-di-F—Ph2-Br-4,6-di-F—Ph NH 380 H Me 2-Cl-6-F—Ph 2-Br-4,6-di-F—Ph NH 381 H Me2-Cl-4-F—Ph 2,6-di-F-4-Cl—Ph CHOH 402 382 H Me 2-F-4-CN—Ph2-Cl-4,6-di-F—Ph NH 383 H Me 2-F-4-CN—Ph 2,6-di-F-4-Cl—Ph NH 384 H Me2-Cl-4-F—Ph 2-Cl-4,6-di-F—Ph CHOH 385 H Me 2,4-di-F—Ph 2-Br-4-F—Ph CHOH386 H Me 2-Cl-4-F—Ph 2-Br-4-F—Ph CHOH 387 H Me 2-Cl-4-OH—Ph 2,4-di-F—PhNH 350 388 H Me 2-Cl-4-OCH₂CN—Ph 2,4-di-F—Ph NH 389 389 H Me 2,4-di-F—Ph4-Br-4-F—Ph NH 396 390 H Me 2,4-di-F—Ph 4-Br-2,6-di-Cl—Ph NH 448 391 HMe 2,4-di-Cl—Ph 2-Cl-4,6-di-F—Ph NH *** 392 H Me 2,4-di-Cl—Ph4-Cl-2,6-di-F—Ph NH *** 393 H Me 2-Cl-4-F—Ph 4-OEt NH 360 394 H Me2-Cl-4-F—Ph 4-Cl-2-F O 369 395 H Me 2,4-di-F—Ph 2-F-4-CN—Ph O 344 396 HMe 2,4-di-F—Ph 4-Cl-2-F—Ph NH 352 397 H Me 2,4-di-F—Ph 2,4-di-Cl-6-F—PhNH 386 398 H Me 2,6-di-F—Ph 4-Cl-2-F—Ph NH 352 399 H Me 2,6-di-F-4-2-F-4-CN—Ph O 445 (OCH₂CH₂CH₂NMe₂)—Ph 400 H Me 4-Cl—Ph 2,6-di-F—Ph NH334 401 H Me 2-Cl-4-F—Ph 4-Cl-2,5-di-F—Ph NH 386 402 H Me 2-Br-4-F—Ph4-Br-2,6-di-F—Ph NH 474 403 H Me 2-Cl-4-F—Ph 4-Br-2,6-di-Cl—Ph NH 464404 H Me 2-Cl-4-F—Ph 2-Cl-4,5-di-F—Ph NH 386 405 H Me 2,4-di-F—Ph2,4,6-tri-Cl—Ph NH 404 406 H Me 2,4-di-F—Ph 2-Br-4,6-di-F—Ph NH 416 407H Me 2,4-di-F—Ph 4-Br-2-Cl—Ph NH 414 408 H Me 2-Br-4-F—Ph4-Br-2,6-di-Cl—Ph NH 508 409 H Me 2-Br-4-F—Ph 4-Br-2-F—Ph NH 458 410 HMe 2-Cl-4-F—Ph 2,4,6-tri-Cl—Ph NH 420 411 H Me 2-Cl-4-F—Ph2-Br-4,6-di-F—Ph NH 432 412 H Me 2-Cl-4-F—Ph 4-Br-2-Cl—Ph NH 430 413 HMe 2-Br-4-F—Ph 4-Br-2-Cl—Ph NH 474 414 H Me 2-Br-4-F—Ph 2,4,6-tri-Cl—PhNH 464 415 H Me 2,4-di-F—Ph 4-F-2-I—Ph NH 444 416 H Me 2,4-di-F—Ph2,4,6-tri-Me—Ph NH 342 417 H Me 2-Cl-4-F—Ph 4-Cl-2,5-di-F—Ph NH 386 418H Me 2-Cl-4-F—Ph 2-Cl-4,5-di-F—Ph NH 386 419 H Me 2-Cl-4-F—Ph2,4-di-F—Ph CHOAc 409 420 H Me 2-Cl-4-F—Ph pyridin-2-yl CHOH 332 421 HMe 2-Cl-4-F—Ph 4-Cl-2-F—Ph CHOH 384 422 H Me 2-Cl-4-F—Ph 2,4,6-tri-F—PhCHOH 385 423 H Me 2-Cl-4-F—Ph 2-F-4-CN—Ph CHOH 374 424 H Me 2,4-di-F—Ph4-Cl-2-F-6-I—Ph NH 478 425 H Me 2-Cl-4- 2,4-di-F—Ph NH 421(OCH₂CH₂CH₂NHMe)—Ph 426 H Me 2-Cl-4- 2,4-di-F—Ph NH 422(OCH₂CH₂CH₂OMe)—Ph 427 H Et 2-Cl-4-F—Ph 2,4-di-F—Ph NH 366 428 H Et2-Cl-4-F—Ph 2,4-di-F—Ph CHOH 382 *¹H NMR data found in Index Table B**AP⁺ data or ¹H NMR data found in the Synthesis Examples ***MP datafound in Index Table C

INDEX TABLE B Cmpd No. ¹H NMR Data (CDCl₃ solution unless indicatedotherwise)^(a) 3 δ 7.11 (m, 1H), 6.99 (m, 1H), 6.75-6.85 (m, 3H), 6.58(m, 1H), 6.40 (m, 1H), 3.58 (s, 3H), 3.07 (s, 3H), 2.21 (s, 3H). ^(a1)HNMR data are in ppm downfield from tetramethylsilane. Couplings aredesignated by (s)-singlet and (m)-multiplet.

INDEX TABLE C Cmpd No. Melting Point ^(b) 110  85-87 111 165-167 112 80-82 113 135-137 114 147-149 115 168-170 123 171-173 124 135-137 125138-140 126 142-144 129 127-130 130 129-131 131 129-133 133 160-162 134228-230 135 112-117 136 152-154 137 165-167 138 171-173 142 186-188 143 93-95 144 176-178 145 142-144 146 145-147 147  60-62 151 150-158 156107-114 157  96-101 164 106-110 165 111-113 178 110-112 179 105-107 180130-132 186  78-84 187 107-113 194 133-135 195  98-100 197 115-117 198106-108 199 134-136 200 139-141 201 109-111 207  57-59 209  92-96 210 73-77 211 110-114 212 130-134 214 105-107 215  90-92 216 152-154 217 72-76 218 112-117 224 132-135 225 123-126 226 139-141 227  99-102 228133-135 229 144-146 231 108-110 242  91-93 243  82-84 244  95-97 245 73-75 246 182-184 247 156-158 249  83-87 250 126-129 256 171-173 257172-174 258 121-124 259 97-100 268 178-180 269  80-85 270 172-176 271132-135 272 132-134 273 152-153 274 141-143 275 168-171 276 115-117 277131-134 278 112-114 281  49-52 289 148-150 290 181-183 291 146-149 293116-118 294 113-115 300 178-180 301 168-170 304 186-191 305 101-105 306134-138 307 161-166 308 142-145 309 118-123 327 118-120 329  98-100 333177-179 334 117-119 337 186-188 339 135-136 340 137-139 341 151-153 353169-171 354 111-113 355  90-92 363 229-231 391 181-183 392 155-157 ^(b)Melting point data are ° C..

Biological Examples of the Invention

General protocol for preparing test suspensions for Tests A-J: the testcompounds were first dissolved in acetone in an amount equal to 3% ofthe final volume and then suspended at the desired concentration (inppm) in acetone and purified water (50/50 mix by volume) containing 250ppm of the surfactant Trem® 014 (polyhydric alcohol esters). Theresulting test suspensions were then used in Tests A-J. Spraying a 200ppm test suspension to the point of run-off on the test plants was theequivalent of a rate of 500 g/ha. Unless otherwise indicated, the ratingvalues indicate a 200 ppm test suspension was used. (An asterisk “*”next to the rating value indicates a 40 ppm test suspension was used.)

Test A

Grape seedlings were inoculated with a spore suspension of Plasmoparaviticola (the causal agent of grape downy mildew) and incubated in asaturated atmosphere at 20° C. for 24 h. After a short drying period,the test suspension was sprayed to the point of run-off on the grapeseedlings and then moved to a growth chamber at 20° C. for 4 days, afterwhich time the test units were placed back into a saturated atmosphereat 20° C. for 24 h. Upon removal, visual disease ratings were made.

Test B

The test suspension was sprayed to the point of run-off on tomatoseedlings. The following day the seedlings were inoculated with a sporesuspension of Botrytis cinerea (the causal agent of tomato Botrytis) andincubated in saturated atmosphere at 20° C. for 48 h, and then moved toa growth chamber at 24° C. for 3 additional days, after which timevisual disease ratings were made.

Test C

The test suspension was sprayed to the point of run-off on tomatoseedlings. The following day the seedlings were inoculated with a sporesuspension of Alternaria solani (the causal agent of tomato earlyblight) and incubated in a saturated atmosphere at 27° C. for 48 h, andthen moved to a growth chamber at 20° C. for 5 days, after which timevisual disease ratings were made.

Test D

The test suspension was sprayed to the point of run-off on tomatoseedlings. The following day the seedlings were inoculated with a sporesuspension of Phytophthora infestans (the causal agent of tomato lateblight) and incubated in a saturated atmosphere at 20° C. for 24 h, andthen moved to a growth chamber at 20° C. for 5 days, after which timevisual disease ratings were made.

Test E

The test suspension was sprayed to the point of run-off on creeping bentgrass (Agrostis sp.) seedlings. The following day the seedlings wereinoculated with a bran and mycelial slurry of Rhizoctonia solani (thecausal agent of turf brown patch) and incubated in a saturatedatmosphere at 27° C. for 48 h, and then moved to a growth chamber at 27°C. for 3 days, after which time disease ratings were made.

Test F

The test suspension was sprayed to the point of run-off on wheatseedlings. The following day the seedlings were inoculated with a sporesuspension of Septoria nodorum (the causal agent of Septoria glumeblotch) and incubated in a saturated atmosphere at 24° C. for 48 h, andthen moved to a growth chamber at 20° C. for 6 days, after which timevisual disease ratings were made.

Test G

The test suspension was sprayed to the point of run-off on wheatseedlings. The following day the seedlings were inoculated with a sporesuspension of Septoria tritici (the causal agent of wheat leaf blotch)and incubated in saturated atmosphere at 24° C. for 48 h. and then theseedlings were moved to a growth chamber at 20° C. for 19 additionaldays, after which time visual disease ratings were made.

Test H

Wheat seedlings were inoculated with a spore suspension of Pucciniarecondita f. sp. tritici (the causal agent of wheat leaf rust) andincubated in a saturated atmosphere at 20° C. for 24 h, and then movedto a growth chamber at 20° C. for 2 days. At the end of this time thetest suspension was sprayed to the point of run-off, and then theseedlings were moved to a growth chamber at 20° C. for 6 days afterwhich time visual disease ratings were made.

Test I

The test suspension was sprayed to the point of run-off on wheatseedlings. The following day the seedlings were inoculated with a sporesuspension of Puccinia recondita f. sp. tritici (the causal agent ofwheat leaf rust) and incubated in a saturated atmosphere at 20° C. for24 h, and then moved to a growth chamber at 20° C. for 7 days, afterwhich time visual disease ratings were made

Test J

The test suspension was sprayed to the point of run-off on wheatseedlings. The following day the seedlings were inoculated with a sporedust of Erysiphe graminis f sp. tritici, (the causal agent of wheatpowdery mildew) and incubated in a growth chamber at 20° C. for 8 days,after which time visual disease ratings were made.

Results for Tests A-J are given in Table A. In the Table, a rating of100 indicates 100% disease control and a rating of 0 indicates nodisease control (relative to the controls). A dash (-) indicates no testresults.

TABLE A Cmpd No. Test A Test B Test C Test D Test E Test F Test G Test HTest I Test J 1 0 99 0 0 47 0 99 — 0 98 2 8 1 0 0 0 0 0 — 0 0 3 6 0 25 90 0 13 — 0 99 4 29 87 46 0 0 0 98 — 53 97 5 36 0 25 0 0 0 0 — 0 0 6 6510 23 0 0 0 0 — 0 93 7 29 99 0 0 63 0 100 — 74 92 8 55 99 54 0 99 0 100— 97 99 9 — 99 0 0 55 0 100 — 98 97 10 — 47 0 0 0 0 0 — 0 0 11 — 99 99 099 0 100 — 99 100 12 — 99 93 0 99 0 100 — 99 100 13 — 99 100 0 98 64 100— 100 99 14 — 98 0 — — 0 99 — 99 98 15 — 99 67 — — 73 99 — 98 99 16 — 600 — — 0 47 48 28 0 17 — 100 100 — — 93 97 96 100 100 18 — 99 100 — — 9995 99 100 100 19 — 100 85 — — 0 96 0 92 98 20 — 100 99 — — 100 100 79100 99 21 — 98 100 — — 97 — — 100 99 22 — 90 85 — — 90 94 9 94 100 23 —98 100 — — 99 93 92 100 100 24 — 98 100 — — 0 94 9 97 100 25 — 100 0 — —0 100 0 94 79 26 — 99 83 — — 0 100 0 99 100 27 — 99 88 — — 0 95 0 25 8728 — 99 0 — — 0 96 7 91 0 29 — 94 0 — — 0 98 0 46 0 30 — 7 0 — — 0 41 079 0 31 —  99* 98* — —  0* 47*  15*  79*  60* 32 — 99 0 — — 0 96 0 99 9733 — 0 0 — — 0 95 0 18 0 34 — 100* 97* — —  0* 96*  0*  76*  0* 35 — 1000 — — 0 95 0 97 100 36 — 100 0 — — 0 96 0 96 98 37 0 0 0 0 0 0 3 — 0 038 — 99 9 — — 0 97 0 99 99 39 — 100 99 — — 0 99 99 99 99 40 — 99 0 — — 094 92 99 99 41 — 100 99 — — 90 94 0 100 99 42 — 100 0 — — 0 93 0 94 8243 — 76 0 — — 0 97 66 82 99 44 — 82 0 — — 0 96 7 9 0 45 — 100 100 — —100 100 7 100 100 46 — 99 100 — — 99 100 37 100 99 47 — 100* 87* — —  0*99*  37*  96*  99* 48 — 100 78 — — 0 99 0 98 98 49 — 100 17 — — 35 99 089 79 50 — 99 57 — — 0 100 0 98 99 51 — 100 0 — — 0 100 0 89 78 52 — 540 — — 0 97 0 92 64 53 — 0 0 — — 0 0 0 0 0 54 — 96 0 — — 0 41 0 95 95 55— 6 0 — — 0 98 0 41 73 56 — 43 0 — — 0 99 0 28 64 57 — 98 0 — — 0 94 8585 0 58 — 98 100 — — 89 98 82 100 100 59 — 94 0 — — 0 88 0 68 0 60 — 750 — — 0 97 59 79 0 61 — 97 0 — — 0 99 0 38 73 62 — 99 98 — — 84 98 98 9999 63 — 0 0 — — 0 0 0 0 0 64 — 97 80 — — 0 100 0 95 98 65 — 0 0 — — 0 10 58 0 66 — 100 99 — — 0 100 6 100 99 67 — 95 0 — — 0 99 24 95 86 68 — 00 — — 0 0 6 0 0 69 — 100 73 — — 60 99 91 99 100 70 — 99 0 — — 0 99 41 8598 71 — 93 0 — — 0 96 0 91 67 72 — 0 0 — — 0 0 59 0 0 73 — 100 99 — — 64100 88 100 99 74 — 0 0 — — 0 25 4 0 0 75 — 100 98 — — 98 99 95 99 97 76— 100 0 — — 0 98 6 0 0 77 — 99 0 — — 0 95 6 97 0 78 — 99 82 — — 0 98 089 91 79 — 99 0 — — 0 99 0 55 0 80 — 100 0 — — 0 99 18 86 89 81 — 97 0 —— 0 0 0 27 0 82 — 100 100 — — 40 99 0 68 13 83 — 100 100 — — 89 99 99 9694 84 — 100 100 — — 78 100 98 100 99 85 — 0 0 — — 0 17 0 19 0 86 — 0 0 —— 0 48 0 0 0 87 — 100 100 — — 95 98 85 99 100 88 — 100 100 — — 99 98 9599 100 89 — 99 0 — — 0 99 0 0 97 90 — 99 95 — — 84 100 0 98 100 91 — 10099 — — 95 99 0 100 100 92 — 100 100 — — 99 100 41 99 100 93 — 41 0 — — 077 0 9 0 94 — 99 70 — — 29 98 0 9 0 95 — 99 16 — — 0 97 0 0 0 96 — 99 99— — 99 100 9 99 100 97 — 100 99 — — 95 100 0 99 99 98 — 100 17 — — 69100 26 99 99 99 — 100 99 — — 100 99 40 100 100 100 — 38 0 — — 0 48 0 410 101 — 100 99 — — 100 100 99 99 100 102 — 100 100 — — 98 99 0 100 98103 — 100 64 — — 0 95 0 91 0 104 — 100 99 — — 97 99 99 99 100 105 — 23 0— — 0 73 9 0 72 106 — 100 99 — — 90 100 82 99 100 107 —  99*  0* — —  0*99*  8*  24*  0* 108 — 97 0 — — 0 98 0 16 97 109 — 100 99 — — 97 100 99100 100 110 — 99 66 — — 98 99 0 97 94 111 — 99 75 — — 90 99 0 97 99 112— 100 98 — — 99 99 53 100 100 113 — 99 47 — — 0 100 8 95 48 114 — 99 24— — 69 99 8 99 84 115 — 99 0 — — 0 100 0 91 0 116 — 100 94 — — 73 100 1697 99 117 — 99 97 — — 82 100 11 98 97 118 — 100 100 — — 98 100 99 100 99119 — 100 0 — — 0 100 16 99 96 120 — 100 99 — — 94 100 0 99 99 121 — 10086 — — 82 99 83 100 97 122 — 0 0 — — 0 0 11 0 0 123 — 99 0 — — 40 99 —80 0 124 — 100 78 — — 60 99 — 96 94 125 — 100 67 — — 60 99 — 92 0 126 —99 96 — — 60 100 0 94 0 127 — 70 0 — — 0 99 0 68 0 128 — 100 100 — — 9799 66 100 100 129 — 99 0 — — 0 96 0 0 0 130 — 97 0 — — 0 99 0 19 0 131 —99 0 — — 0 98 0 86 94 132 — 99 0 — — 0 100 0 94 92 133 — 100 100 — — 6099 0 100 94 134 — 99 0 — — 0 99 0 41 0 135 — 0 0 — — 0 97 16 74 95 136 —99 71 — — 86 99 0 99 100 137 — 96 97 — — 78 99 8 100 100 138 — 99 96 — —84 99 38 100 98 139 — 100 86 — — 100 100 69 99 100 140 — 99 94 — — 87 990 96 97 141 — 99 99 — — 98 100 0 99 100 142 — 33 13 — — 20 99 0 95 90143 — 99 99 — — 100 100 63 100 100 144 — 99 9 — — 40 99 0 98 91 145 — 9698 — — 100 100 88 100 100 146 — 99 0 — — 0 99 0 97 56 147 — 99 88 — —100 100 0 98 92 148 — 99 99 — — 100 100 61 100 99 149 — 100 98 — — 100100 99 100 100 150 — 19 0 — — 60 7 0 74 50 151 — 99 9 — — 0 96 0 54 64152 — 100 82 — — 87 99 9 97 99 153 — 100 0 — — 73 100 0 96 98 154 — 9999 — — 97 100 41 100 100 155 — 100 99 — — 100 100 92 100 99 156 — 94 0 —— 0 73 0 41 47 157 — 0 0 — — 0 0 0 54 73 158 — 100 0 — — 0 99 18 99 98159 — 99 0 — — 0 100 74 99 100 160 — 98 99 — — 0 99 8 100 100 161 — 98100 — — 0 100 95 100 98 162 — 99 0 — — 0 99 8 98 94 163 — 0 9 — — 0 83 088 0 164 — 49 57 — — 0 99 15 9 97 165 — 0 0 — — 0 52 8 0 99 166 — 0 0 —— 0 97 0 68 96 167 — 75 0 — — 0 0 0 0 0 168 — 14 0 — — 0 33 0 0 0 169 —24 0 — — 0 85 0 0 0 170 — 100 99 — — 99 98 0 100 99 171 — 100 97 — — 097 68 99 100 172 — 100 100 — — 87 100 0 99 100 173 — 100 86 — — 0 98 083 100 174 — 100 99 — — 0 96 0 97 99 175 — 100 99 — — 82 96 93 99 100176 — 100 71 — — 0 96 0 68 100 177 — 100 100 — — 73 98 0 83 100 178 —100 100 — — 80 98 0 83 100 179 — 100 99 — — 73 95 0 93 100 180 — 100 99— — 0 98 0 68 100 181 — 94 44 — — 0 100 0 60 98 182 — 97 99 — — 87 100 095 99 183 — 97 100 — — 67 99 27 94 99 184 — 97 0 — — 0 99 0 82 98 185 —0 0 — — 0 100 0 74 98 186 — 0 0 — — 0 99 0 54 93 187 — 33 0 — — 0 20 0 913 188 — 87 0 — — 0 100 0 97 97 189 — 99 100 — — 80 100 99 99 98 190 —99 99 — — 80 100 94 100 99 191 — 98 100 — — 0 100 0 97 99 192 — 97 100 —— 73 100 0 99 99 193 — 99 100 — — 0 100 32 99 100 194 — 97 86 — — 0 99 091 99 195 — 100 97 — — 60 100 0 98 97 196 — 99 94 — — 73 100 9 98 98 197— 97 0 — — 95 99 0 79 96 198 — 97 68 — — 0 100 0 94 97 199 — 99 86 — — 099 0 68 98 200 — 82 0 — — 0 97 0 0 94 201 — 99 97 — — 20 100 18 97 99202 — 99 0 — — 0 99 0 28 99 203 — 99 0 — — 0 98 0 96 100 204 — 100* 77*— —  0* 99*  0*  86*  99* 205 — 100 17 — — 0 99 0 91 100 206 — 99 99 — —84 99 41 99 100 207 — 100 93 — — 64 100 0 99 100 208 — 100 100 — — 99100 0 99 99 209 — 0 0 — — 0 0 0 0 97 210 — 0 0 — — 0 100 99 94 99 211 —77 0 — — 0 99 0 17 96 212 — 0 17 — — — 98 0 — — 213 — 97 30 — — 0 85 9496 100 214 — 98 51 — — 0 100 9 99 100 215 — 89 0 — — 0 98 0 94 99 216 —96 0 — — 0 76 0 26 99 217 — 75 0 — — 0 83 40 79 99 218 — 94 0 — — 0 9917 92 87 219 — 70 0 — — 0 0 17 0 0 220 — 98 97 — — 40 98 40 99 100 221 —98 94 — — 82 100 17 99 100 222 — 99 99 — — 0 100 88 99 100 223 — 96 9 —— 99 100 0 100 100 224 — 99 51 — — 0 100 17 91 100 225 — 65 0 — — 0 99 079 98 226 — 99 0 — — 0 96 28 91 100 227 — 87 0 — — 0 99 0 74 98 228 — 9999 — — 0 99 0 80 99 229 — 99 17 — — 0 99 0 91 98 230 — 99 99 — — 0 100 097 100 231 — 98 34 — — 0 100 0 86 100 232 — 100 99 — — 99 100 0 100 100233 — 100 99 — — 99 100 0 100 100 234 — 99 0 — — 0 99 0 92 84 235 — 84 0— — 0 17 0 0 79 236 — 97 0 — — 0 96 0 68 97 237 — 99 0 — — 0 97 0 68 97238 — 99 0 — — 0 0 53 9 43 239 — 99 95 — — 0 67 0 68 100 240 — 100 99 —— 0 99 0 99 100 241 — 99 99 — — 0 100 97 100 100 242 — 99 37 — — 0 100 091 100 243 — 100 64 — — 0 100 0 97 100 244 — 82 0 — — 0 91 0 0 96 245 —90 0 — — 0 97 0 68 93 246 — 99 51 — — 0 100 0 80 100 247 — 100 99 — — 60100 0 99 100 248 — 99 26 — — 73 100 0 99 100 249 — 40 0 — — 0 99 0 96100 250 — 98 0 — — 0 77 0 86 100 251 — 99 0 — — 0 98 0 86 100 252 — 10097 — — 0 100 0 100 100 253 — 99 0 — — 0 0 0 0 76 254 — 100 0 — — 0 84 00 64 255 — 100 0 — — 0 0 0 0 39 256 — 99 99 — — 96 100 0 99 100 257 —100 99 — — 0 100 0 97 98 258 — 41 9 — — 0 89 0 68 90 259 — 98 9 — — 0100 0 86 97 260 — 0 0 — — 0 0 0 0 0 261 — 0 0 — — 0 0 0 0 47 262 — 99 51— — 0 0 0 68 99 263 — 100 98 — — 0 100 0 98 100 264 — 100 98 — — 0 92 099 98 265 — 100 99 — — 78 100 90 100 100 266 — 100 100 — — 98 100 0 100100 267 — 100 79 — — 60 100 0 96 93 268 — 95 93 — — 0 99 0 74 0 269 — 800 — — 0 67 8 0 0 270 — 92 86 — — 0 91 8 0 81 271 — 100 99 — — 99 100 099 98 272 — 100 97 — — 99 99 0 99 99 273 — 0 0 — — 0 72 0 27 43 274 — 80 — — 0 96 8 0 69 275 — 97 46 — — 0 99 8 97 99 276 — 100 99 — — 98 10031 100 100 277 — 100 0 — — 0 100 0 96 98 278 — 99 0 — — 0 99 0 82 100279 — 100 99 — — 0 100 8 98 100 280 — 99 0 — — 0 96 8 18 87 281 — 98 44— — 0 — 0 94 98 282 — 99 98 — — 0 — 0 99 100 283 — 99 65 — — 0 — 9 99100 284 — 99 99 — — 100 — 28 100 100 285 — 98 0 — — 60 — 9 99 99 286 — 98* 85* — — 60* — 100* 100* 100* 288 9 99 52 0 92 0 — — 74 92 289 — 1000 — — 0 99 0 96 97 290 — 100 99 — — 87 100 0 100 100 291 — 99 0 — — 0 980 85 43 292 — 100 99 — — 96 100 92 100 100 293 0 97 47 0 99 0 — — 94 99294 0 98 0 0 80 0 — — 0 84 296 — 99 0 — — 0 100 0 99 — 297 — 100 99 — —90 100 0 100 100 298 — 100 93 — — 87 100 0 100 100 299 — 100 95 — — 5141 100 100 300 — 100 99 — — 82 100 9 99 100 301 — 99 87 — — 87 100 0 9899 302 —  99*  0* — —  0* 99*  0*  18*  97* 303 — 99 0 — — 0 98 0 92 71304 — 0 0 — 0 0 16 — 0 0 305 — 99 99 — — 94 100 0 99 99 306 — 7 0 — — 093 0 28 64 307 — 0 0 — — 0 0 0 0 0 308 — 81 0 — — 0 98 9 100 0 309 — 9761 — 92 60 100 — 0 99 310 — 100 99 — — 99 100 0 99 96 311 — 100 0 — — 60100 0 99 91 313 — 100 97 — — 51 100 91 100 100 314 — 100 95 — — 0 100 94100 100 315 — 99 99 — — 0 100 0 96 100 316 — 99 0 — — 0 — 9 99 96 318 —99 0 — — 0 100 0 97 89 319 — 92 88 — — 100 100 0 99 95 320 — 99 67 — — 0100 0 99 98 321 — 100 99 — — 78 100 9 99 100 322 — 100 93 — — 0 100 99100 100 323 — 98 0 — — 0 98 0 94 — 324 — 99 83 — — 0 100 63 99 99 325 —100 0 — — 0 100 0 97 99 326 8 99 99 0 99 73 100 — 99 94 327 — 99 0 — — 0100 0 96 99 328 — 100 86 — — 0 100 0 98 100 329 — 100 99 — — 69 100 0100 100 331 — 100 80 — — 73 100 8 100 97 333 — 100 0 — — 0 100 9 74 0334 — 100 0 — — 0 100 0 97 100 336 — 100 97 — — 95 100 94 100 99 337 —99 0 — — 0 99 9 41 98 338 — 100 37 — — 40 100 8 100 99 339 — 100 0 — — 0100 0 98 100 340 — 99 0 — — 0 100 0 91 100 341 — 99 0 — — 0 99 0 99 93342 — 100 33 — — 99 100 0 100 100 343 — 100 100 — — 97 100 91 100 100344 — 100 40 — — 87 100 62 100 100 345 — 0 0 — — 0 67 0 9 0 348 — 100 80— — 94 100 19 100 100 350 — 99 9 — — 0 — 9 96 0 351 — 100 99 — — 92 — 96100 99 353 — 97 17 — — 0 99 3 99 99 354 — 99 0 — — 0 100 82 98 100 355 —99 0 — — 0 100 3 91 0 356 — 100 0 — — 0 — 100 100 0 357 — 100 86 — — 87100 0 99 100 358 — 99 0 — — 0 100 0 97 97 359 — 100 99 — — 97 100 0 10099 360 — 100 97 — — 95 100 79 100 100 361 — 100 90 — — 0 100 0 100 100362 — 100 0 — — 0 100 0 96 96 363 — 65 0 — — 0 99 0 96 43 364 — 99 97 —— 88 100 0 99 100 365 — 100 99 — — 64 100 74 100 100 366 — 100 58 — — 0100 9 99 100 367 — 100 100 — — 100 — 100 100 100 369 — 100 66 — — 0 — 17100 99 389 — 100 9 — — 0 — 68 98 99 391 — 100 99 — — 73 — 31 99 99 403 —99 0 — — 0 — 99 100 99 “Cmpd No. ” means compound number and refers tothe same compound number as in Index Table A.

What is claimed is:
 1. A compound selected from Formula 1, N-oxides andsalts thereof,

wherein Q¹ is a phenyl ring or a naphthalenyl ring system, each ring orring system optionally substituted with up to 5 substituentsindependently selected from R³; or a 5- to 6-membered fully unsaturatedheterocyclic ring or an 8- to 10-membered heteroaromatic bicyclic ringsystem, each ring or ring system containing ring members selected fromcarbon atoms and up to 4 heteroatoms independently selected from up to 2O, up to 2 S and up to 4 N atoms, wherein up to 3 carbon ring membersare independently selected from C(═O) and C(═S), and the sulfur atomring members are independently selected from S(═O)_(u)(═NR¹⁴)_(v), eachring or ring system optionally substituted with up to 5 substituentsindependently selected from R³ on carbon atom ring members and selectedfrom cyano, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆ cycloalkyl,C₁-C₆ alkoxy, C₂-C₆ alkoxyalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆ alkylaminoalkyl and C₃-C₆ dialkylaminoalkyl onnitrogen atom ring members; Q² is a phenyl ring or a naphthalenyl ringsystem, each ring or ring system optionally substituted with up to 5substituents independently selected from R³; or a 5- to 6-memberedsaturated, partially unsaturated or fully unsaturated heterocyclic ringor an 8- to 10-membered heteroaromatic bicyclic ring system, each ringor ring system containing ring members selected from carbon atoms and upto 4 heteroatoms independently selected from up to 2 O, up to 2 S and upto 4 N atoms, wherein up to 3 carbon ring members are independentlyselected from C(═O) and C(═S), and the sulfur atom ring members areindependently selected from S(═O)_(u)(═NR¹⁴)_(v), each ring or ringsystem optionally substituted with up to 5 substituents independentlyselected from R³ on carbon atom ring members and selected from cyano,C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆ cycloalkyl, C₁-C₆alkoxy, C₂-C₆ alkoxyalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl,C₂-C₆ alkylaminoalkyl and C₃-C₆ dialkylaminoalkyl on nitrogen atom ringmembers; or C₁-C₁₂ alkyl, C₂-C₁₂ alkenyl, C₂-C₁₂ alkynyl, C₃-C₁₂cycloalkyl or C₃-C₁₂ cycloalkenyl, each optionally substituted with upto 5 substituents independently selected from R³; X is O, S(O)_(m), NR⁴,CR¹⁵R¹⁶, C(═O) or C(═S); R¹ is H, halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl,C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₃-C₇ cycloalkyl, CO₂R⁵, C(O)NR⁶R⁷, cyano,C₁-C₆ alkoxy, C₁-C₆ haloalkoxy or C₂-C₅ alkoxyalkyl; or R¹ is phenyloptionally substituted with up to 3 R⁸; or a five- or six-memberednitrogen-containing aromatic heterocycle optionally substituted with upto 3 substituents independently selected from R^(9a) on carbon atom ringmembers and R^(9b) on nitrogen atom ring members; R^(1a) is H; or R^(1a)and R¹ are taken together with the carbon atom to which they areattached to form a cyclopropyl ring optionally substituted with up to 2substituents independently selected from halogen and methyl; R² is CH₃,CH₂CH₃, halogen, cyano, cyanomethyl, halomethyl, hydroxymethyl, methoxyor methylthio; or cyclopropyl optionally substituted with up to 2substituents independently selected from halogen and methyl; each R³ isindependently selected from halogen, cyano, nitro, amino, methylamino,dimethylamino, formylamino, C₂-C₃ alkylcarbonylamino, C₁-C₄ alkyl, C₁-C₄haloalkyl, C₁-C₃ alkoxy, C₁-C₃ haloalkoxy, C₁-C₃ alkylthio, C₁-C₃haloalkylthio, C₁-C₃ alkylsulfinyl, C₁-C₃ haloalkylsulfinyl, C₁-C₃alkylsulfonyl, C₁-C₃ haloalkylsulfonyl, C₁-C₂ alkylsulfonyloxy, C₁-C₂haloalkylsulfonyloxy, C₃-C₄ cycloalkyl, C₃-C₇ cycloalkoxy, C₄-C₆alkylcycloalkyl, C₄-C₆ cycloalkylalkyl, C₃-C₇ halocycloalkyl, C₂-C₄alkenyl, C₂-C₄ alkynyl, hydroxy, formyl, C₂-C₃ alkylcarbonyl, C₂-C₃alkylcarbonyloxy, —SF₅, —SCN, C(═S)NR¹⁹R²⁰ or —U—V-T; R⁴ is H, formyl,C₂-C₅ alkenyl, C₃-C₅ alkynyl, C₃-C₇ cycloalkyl, —SO₃-M⁺, —S(═O)_(t)R¹⁰,—(C═W)R¹¹, NH₂ or OR²¹; or C₁-C₆ alkyl or C₁-C₆ haloalkyl, eachoptionally substituted with up to 2 R¹²; R⁵ is H, C₁-C₆ alkyl or C₁-C₆haloalkyl; R⁶ and R⁷ are independently selected from H, C₁-C₆ alkyl,C₁-C₆ haloalkyl, C₃-C₇ cycloalkyl, C₄-C₈ cycloalkylalkyl and C₄-C₈alkylcycloalkyl; or R⁶ and R⁷ are taken together with the nitrogen atomto which they are connected to form a four- to seven-memberednonaromatic heterocyclic ring containing ring members, in addition tothe connecting ring nitrogen atom, selected from carbon atoms andoptionally up to one ring member selected from O, S(O)_(n) and NR¹³;each R⁸, R^(9a) and R^(9b) is independently selected from halogen, C₁-C₂alkyl, C₁-C₂ haloalkyl, C₁-C₂ alkoxy, C₁-C₂ haloalkoxy, cyano, nitro,SCH₃, S(O)CH₃ and S(O)₂CH₃; R¹⁰ is C₁-C₆ alkyl or C₁-C₆ haloalkyl; eachR¹¹ is independently C₁-C₆ alkyl, C₁-C₆ alkoxy, C₂-C₇ alkoxyalkyl, C₂-C₇alkylaminoalkyl, C₂-C₈ dialkylaminoalkyl, C₁-C₆ alkylthio or C₂-C₇alkylthioalkyl; each R¹² is independently C₃-C₇ cycloalkyl, C₁-C₄alkoxy, C₁-C₄ haloalkoxy, C₁-C₄ alkylthio, C₁-C₄ alkylsulfinyl, C₁-C₄alkylsulfonyl or cyano; R¹³ is H, C₁-C₃ alkyl or C₂-C₃ haloalkyl; eachR¹⁴ is independently H, cyano, C₁-C₃ alkyl or C₁-C₃ haloalkyl; R¹⁵ is H,C₁-C₄ alkyl or OR¹⁸; R¹⁶ is C₁-C₄ alkyl or OR¹⁸; or R¹⁵ and R¹⁶ aretaken together as —OCH₂CH₂O—; each R¹⁸ is independently H, formyl, C₃-C₇cycloalkyl, —SO₃ ⁻M⁺ or —(C═W)R¹¹; or C₁-C₆ alkyl or C₁-C₆ haloalkyl,each optionally substituted with up to 2 R¹²; each R¹⁹ and R²⁰ isindependently H or CH₃; R²¹ is H, formyl, C₃-C₇ cycloalkyl, —SO₃ ⁻M⁺ or—(C═W)R¹¹; or C₁-C₆ alkyl or C₁-C₆ haloalkyl, each optionallysubstituted with up to 2 R¹²; each U is independently O, S(═O)_(w), NR²²or a direct bond; each V is independently C₁-C₆ alkylene, C₂-C₆alkenylene, C₃-C₆ alkynylene, C₃-C₆ cycloalkylene or C₃-C₆cycloalkenylene, wherein up to 3 carbon atoms are independently selectedfrom C(═O), each optionally substituted with up to 5 substituentsindependently selected from halogen, cyano, nitro, hydroxy, C₁-C₆ alkyl,C₁-C₆ haloalkyl, C₁-C₆ alkoxy and C₁-C₆ haloalkoxy; each T isindependently cyano, NR^(23a)R^(23b), OR²⁴ or S(═O)_(y)R²⁵ each R²² isindependently H, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkylcarbonyl,C₂-C₆ alkoxycarbonyl, C₂-C₆ (alkylthio)carbonyl, C₂-C₆alkoxy(thiocarbonyl), C₄-C₈ cycloalkylcarbonyl, C₄-C₈cycloalkoxycarbonyl, C₄-C₈ (cycloalkylthio)carbonyl or C₄-C₈cycloalkoxy(thiocarbonyl); each R^(23a) and R^(23b) is independently H,C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl, C₃-C₆ alkynyl, C₃-C₆cycloalkyl, C₃-C₆ halocycloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆ (alkylthio)carbonyl, C₂-C₆ alkoxy(thiocarbonyl),C₄-C₈ cycloalkylcarbonyl, C₄-C₈ cycloalkoxycarbonyl, C₄-C₈(cycloalkylthio)carbonyl or C₄-C₈ cycloalkoxy(thiocarbonyl); or a pairof R^(23a) and R^(23b) attached to the same nitrogen atom are takentogether with the nitrogen atom to form a 3- to 6-membered heterocyclicring, the ring optionally substituted with up to 5 substituentsindependently selected from R²⁶; each R²⁴ and R²⁵ is independently H,C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl, C₃-C₆ alkynyl, C₃-C₆cycloalkyl, C₃-C₆ halocycloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆ (alkylthio)carbonyl, C₂-C₆ alkoxy(thiocarbonyl),C₄-C₈ cycloalkylcarbonyl, C₄-C₈ cycloalkoxycarbonyl, C₄-C₈(cycloalkylthio)carbonyl or C₄-C₈ cycloalkoxy(thiocarbonyl); each R²⁶ isindependently halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl or C₁-C₆ alkoxy;each W is independently O or S; each M⁺ is independently a cation; m is0, 1 or 2; n is 0, 1 or 2; t is 0, 1 or 2; each u and v areindependently 0, 1 or 2 in each instance of S(═O)_(u)(═NR¹⁴)_(v),provided that the sum of u and v is 0, 1 or 2; each w is independently0, 1 or 2; and each y is independently 0, 1 or 2; provided that: when Q²is a phenyl ring substituted on at least one ortho position with asubstituent selected from —U—V-T wherein U is a direct bond, V is C(═O)and T is NR^(23a)R^(23b) or OR²⁴, then X is other than NR⁴.
 2. Acompound of claim 1 wherein: Q¹ is phenyl, pyridinyl, pyrimidinyl,pyrazinyl or pyridazinyl, each substituted with from 1 to 4 substituentsindependently selected from R³; provided that when an R³ substituent islocated at a meta position, then said R³ substituent is selected from F,Cl, Br and cyano; Q² is phenyl, pyridinyl, pyrimidinyl, pyrazinyl orpyridazinyl, each substituted with 1, 2 or 3 substituents independentlyselected from R³, provided that when an R³ substituent is located at ameta position, then said R³ substituent is selected from F, Cl, Br andcyano; X is O, NR⁴, C(═O) or CR¹⁵R¹⁶; R¹ is H, halogen, C₁-C₆ alkyl,C₁-C₆ haloalkyl, CO₂R⁵, C(O)NR⁶R⁷, cyano, C₁-C₆ alkoxy, C₁-C₆ haloalkoxyor C₂-C₅ alkoxyalkyl; R^(1a) is H; R² is CH₃, CH₂CH₃, Cl or Br; each R³is independently selected from halogen, cyano, nitro, amino,methylamino, dimethylamino, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₃ alkoxy,C₁-C₃ haloalkoxy C₁-C₃ alkylthio, C₁-C₃ haloalkylthio, C₁-C₃alkylsulfinyl, C₁-C₃ haloalkylsulfinyl, C₁-C₃ alkylsulfonyl, C₁-C₃haloalkylsulfonyl, C₃-C₄ cycloalkyl, C(═S)NH₂ and —U—V-T; R⁴ is H,formyl, C₃-C₇ cycloalkyl or —SR¹⁰; or C₁-C₆ alkyl or C₁-C₆ haloalkyl,each optionally substituted with up to 2 R¹²; R⁵ is C₁-C₆ alkyl; R⁶ is Hor C₁-C₆ alkyl; R⁷ is H, C₁-C₆ alkyl, C₁-C₆ haloalkyl or C₄-C₈alkylcycloalkyl; or R⁶ and R⁷ are taken together with the nitrogen atomto which they are connected to form a four- to seven-memberednonaromatic heterocyclic ring containing ring members, in addition tothe connecting nitrogen atom, selected from carbon atoms and up to onering member selected from O and NR¹³; each R¹² is independently C₃-C₇cycloalkyl, C₁-C₄ alkoxy or cyano; R¹³ is H or CH₃; R¹⁵ is H or CH₃; andR¹⁶ is OR¹⁸.
 3. A compound of claim 2 wherein Q¹ is phenyl or pyridinyl,each substituted with 1, 2 or 3 substituents independently selected fromR³; Q² is phenyl or pyridinyl, each substituted with 1, 2 or 3substituents independently selected from R³; R¹ is H, halogen or C₁-C₆alkyl; R² is CH₃, Cl or Br; each R³ is independently selected fromhalogen, cyano, nitro, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₃ alkoxy, C₁-C₃haloalkoxy and —U—V-T; R⁴ is H, formyl, C₃-C₇ cycloalkyl or —SR¹⁰; orC₁-C₆ alkyl substituted with one R¹²; each R¹² is independentlycyclopropyl, —OCH₃ or cyano; R¹⁵ is H; each U is independently O or NH;each V is C₂-C₄ alkylene; each T is independently NR^(23a)R^(23b) orOR²⁴; each R^(23a) and R^(23b) is independently H, C₁-C₆ alkyl or C₁-C₆haloalkyl; and each R²⁴ is independently H, C₁-C₆ alkyl or C₁-C₆haloalkyl.
 4. A compound of claim 3 wherein at least one of Q¹ and Q² isphenyl substituted with 2 or 3 substituents independently selected fromR³; R¹ is H or CH₃; R² is CH₃; R⁴ is H; each R³ is independentlyselected from halogen, cyano, C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₁-C₃ alkoxyand C₁-C₃ haloalkoxy; and R¹⁸ is H.
 5. A compound of claim 4 wherein Q¹is phenyl substituted at the 2-, 4- and 6-positions with substituentsindependently selected from R³; or phenyl substituted at the 2- and4-positions with substituents independently selected from R³; or phenylsubstituted at the 2- and 6-positions with substituents independentlyselected from R³; Q² is phenyl substituted at the 2-, 4- and 6-positionswith substituents independently selected from R³; or phenyl substitutedat the 2- and 4-positions with substituents independently selected fromR³; or phenyl substituted at the 2- and 6-positions with substituentsindependently selected from R³; X is O, NR⁴ or CR¹⁵R¹⁶; R¹ is H; each R³is independently selected from F, Cl, Br, cyano, C₁-C₂ alkyl, C₁-C₂haloalkyl, C₁-C₂ alkoxy and C₁-C₂ haloalkoxy; and R⁴ is H.
 6. A compoundof claim 5 wherein each R³ is independently selected from F, Cl, Br,cyano, methyl, C₁-C₂ alkoxy and fluoromethoxy.
 7. A compound of claim 6wherein X is O or NH; and each R³ is independently selected from F, Cl,Br, cyano and methoxy.
 8. A compound of claim 1 which is selected fromthe group:4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-N-(2,4,6-trifluorophenyl)-1H-pyrazol-5-amine,N-(4-chlorophenyl)-4-(2,6-difluoro-4-methoxyphenyl)-1,3-dimethyl-1H-pyrazol-5-amine,4-(2,6-difluoro-4-methoxyphenyl)-N-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,4-(2,6-difluoro-4-methoxyphenyl)-1,3-dimethyl-N-(2,4,6-trifluorophenyl)-1H-pyrazol-5-amine,N-(2,6-difluoro-4-methoxyphenyl)-4-(3,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,4-(2,4-difluorophenyl)-1,3-dimethyl-N-(2,4,6-trifluorophenyl)-1H-pyrazol-5-amine,4-[[4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-yl]oxy]-3,5-difluorobenzonitrile,4-[[4-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-yl]oxy]-3-fluorobenzonitrile,4-(2-chloro-4-fluorophenyl)-N-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,4-[[4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-yl]oxy]-3-fluorobenzonitrile,3-chloro-4-[[4-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-yl]oxy]benzonitrile,4-(2-chloro-4-fluorophenyl)-α-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazole-5-methanol,N,4-bis(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,N-(2-chloro-4-fluorophenyl)-4-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,N-(2-chloro-4,6-difluorophenyl)-4-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,N-(2-chloro-4,6-difluorophenyl)-4-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,N-(4-chloro-2,6-difluorophenyl)-4-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,N-(4-chloro-2,6-difluorophenyl)-4-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,3-chloro-4-[[4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-yl]oxy]benzonitrile,4-[[4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-yl]amino]-3,5-difluorobenzonitrile,4-[[4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-yl]oxy]-2,5-difluorobenzonitrile,N-(2-chloro-4-fluorophenyl)-4-(2,6-difluoro-4-methoxyphenyl)-1,3-dimethyl-1H-pyrazol-5-amine,α,4-bis(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-methanol,N-(4-chloro-2,6-difluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine,N-(2-chloro-4,6-difluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,N-(2,6-dichloro-4-fluorophenyl)-4-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,3-chloro-4-[5-[(2-chloro-4,6-difluorophenyl)amino]-1,3-dimethyl-1H-pyrazol-4-yl]-benzonitrile,3-chloro-4-[5-[(4-chloro-2,6-difluorophenyl)amino]-1,3-dimethyl-1H-pyrazol-4-yl]-benzonitrile,N-(2-bromo-4-fluorophenyl)-4-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,4-(2-chloro-4-fluorophenyl)-N-(2,4-dichloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,4-(2-chloro-4-fluorophenyl)-N-(2,6-dichloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,4-[[4-(2-bromo-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-yl]oxy]-3-fluorobenzonitrile,N-(2-bromo-4-fluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,4-(2-bromo-4-fluorophenyl)-1,3-dimethyl-N-(2,4,6-trifluorophenyl)-1H-pyrazol-5-amine,N-(4-bromo-2,6-difluorophenyl)-4-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,4-[[4-(2-bromo-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-yl]oxy]-3,5-difluorobenzonitrile,4-(2-bromo-4-fluorophenyl)-N-(2-chloro-4,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,4-(2-bromo-4-fluorophenyl)-N-(4-chloro-2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,N-(4-bromo-2,6-difluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,3-bromo-4-[[4-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-yl]oxy]benzonitrile,3-chloro-4-[[4-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-yl]oxy]benzonitrile,N-(2,4-dichloro-6-fluorophenyl)-4-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,N-(2,6-dichloro-4-fluorophenyl)-4-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,N-(2-bromo-4,6-difluorophenyl)-4-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,N-(2-bromo-4,6-difluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,N-(4-bromo-2,6-difluorophenyl)-4-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,N-(2-bromo-4,6-difluorophenyl)-4-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,N-(2-bromo-4,6-difluorophenyl)-4-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine,α-(4-chloro-2,6-difluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-methanol,4-[5-[(2-chloro-4,6-difluorophenyl)amino]-1,3-dimethyl-1H-pyrazol-4-yl]-3-fluorobenzonitrile,4-[5-[(4-chloro-2,6-difluorophenyl)amino]-1,3-dimethyl-1H-pyrazol-4-yl]-3-fluorobenzonitrile,α-(2-chloro-4,6-difluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-methanol,α-(2-bromo-4-fluorophenyl)-4-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazole-5-methanol,andα-(2-bromo-4-fluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-methanol.9. The compound of claim 1 which is4-(2,6-difluoro-4-methoxyphenyl)-1,3-dimethyl-N-(2,4,6-trifluorophenyl)-1H-pyrazol-5-amine.10. A fungicidal composition comprising (a) a compound of claim 1; and(b) at least one other fungicide.
 11. A fungicidal compositioncomprising: (a) a compound of claim 1; and (b) at least one additionalcomponent selected from the group consisting of surfactants, soliddiluents and liquid diluents.
 12. A method for controlling plantdiseases caused by fungal plant pathogens comprising applying to theplant or portion thereof, or to the plant seed, a fungicidally effectiveamount of a compound of claim
 1. 13. A composition comprising a compoundof claim 1, and at least one invertebrate pest control compound oragent.
 14. A compound of Formula 2 or a salt thereof

wherein Q¹ is a phenyl ring or a naphthalenyl ring system, each ring orring system optionally substituted with up to 5 substituentsindependently selected from R³; or a 5- to 6-membered fully unsaturatedheterocyclic ring or an 8- to 10-membered heteroaromatic bicyclic ringsystem, each ring or ring system containing ring members selected fromcarbon atoms and up to 4 heteroatoms independently selected from up to 2O, up to 2 S and up to 4 N atoms, wherein up to 3 carbon ring membersare independently selected from C(═O) and C(═S), and the sulfur atomring members are independently selected from S(═O)_(u)(═NR¹⁴)_(v), eachring or ring system optionally substituted with up to 5 substituentsindependently selected from R³ on carbon atom ring members and selectedfrom cyano, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆ cycloalkyl,C₁-C₆ alkoxy, C₂-C₆ alkoxyalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆ alkylaminoalkyl and C₃-C₆ dialkylaminoalkyl onnitrogen atom ring members; Q² is a phenyl ring or a naphthalenyl ringsystem, each ring or ring system optionally substituted with up to 5substituents independently selected from R³; or a 5- to 6-memberedsaturated, partially unsaturated or fully unsaturated heterocyclic ringor an 8- to 10-membered heteroaromatic bicyclic ring system, each ringor ring system containing ring members selected from carbon atoms and upto 4 heteroatoms independently selected from up to 2 O, up to 2 S and upto 4 N atoms, wherein up to 3 carbon ring members are independentlyselected from C(═O) and C(═S), and the sulfur atom ring members areindependently selected from S(═O)_(u)(═NR¹⁴)_(v), each ring or ringsystem optionally substituted with up to 5 substituents independentlyselected from R³ on carbon atom ring members and selected from cyano,C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆ cycloalkyl, C₁-C₆alkoxy, C₂-C₆ alkoxyalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl,C₂-C₆ alkylaminoalkyl and C₃-C₆ dialkylaminoalkyl on nitrogen atom ringmembers; or C₁-C₁₂ alkyl, C₂-C₁₂ alkenyl, C₂-C₁₂ alkynyl, C₃-C₁₂cycloalkyl or C₃-C₁₂ cycloalkenyl, each optionally substituted with upto 5 substituents independently selected from R³; X is NH; R² is CH₃,CH₂CH₃, halogen, cyano, cyanomethyl, halomethyl, hydroxymethyl, methoxyor methylthio; or cyclopropyl optionally substituted with up to 2substituents independently selected from halogen and methyl; each R³ isindependently selected from halogen, cyano, nitro, amino, methylamino,dimethylamino, formylamino, C₂-C₃ alkylcarbonylamino, C₁-C₄ alkyl, C₁-C₄haloalkyl, C₁-C₃ alkoxy, C₁-C₃ haloalkoxy, C₁-C₃ alkylthio, C₁-C₃haloalkylthio, C₁-C₃ alkylsulfinyl, C₁-C₃ haloalkylsulfinyl, C₁-C₃alkylsulfonyl, C₁-C₃ haloalkylsulfonyl, C₁-C₂ alkylsulfonyloxy, C₁-C₂haloalkylsulfonyloxy, C₃-C₄ cycloalkyl, C₃-C₇ cycloalkoxy, C₄-C₆alkylcycloalkyl, C₄-C₆ cycloalkylalkyl, C₃-C₇ halocycloalkyl, C₂-C₄alkenyl, C₂-C₄ alkynyl, hydroxy, formyl, C₂-C₃ alkylcarbonyl, C₂-C₃alkylcarbonyloxy, —SF₅, —SCN, C(═S)NR¹⁹R²⁰ or —U—V-T; each R¹⁴ isindependently H, cyano, C₁-C₃ alkyl or C₁-C₃ haloalkyl; each R¹⁹ and R²⁰is independently H or CH₃; each U is independently O, S(═O)_(w), NR²² ora direct bond; each V is independently C₁-C₆ alkylene, C₂-C₆ alkenylene,C₃-C₆ alkynylene, C₃-C₆ cycloalkylene or C₃-C₆ cycloalkenylene, whereinup to 3 carbon atoms are independently selected from C(═O), eachoptionally substituted with up to 5 substituents independently selectedfrom halogen, cyano, nitro, hydroxy, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆alkoxy and C₁-C₆ haloalkoxy; each T is independently cyano,NR^(23a)R^(23b), OR²⁴ or S(═O)_(y)R²⁵ each R²² is independently H, C₁-C₆alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-C₆(alkylthio)carbonyl, C₂-C₆ alkoxy(thiocarbonyl), C₄-C₈cycloalkylcarbonyl, C₄-C₈ cycloalkoxycarbonyl, C₄-C₈(cycloalkylthio)carbonyl or C₄-C₈ cycloalkoxy(thiocarbonyl); eachR^(23a) and R^(23b) is independently H, C₁-C₆ alkyl, C₁-C₆ haloalkyl,C₂-C₆ alkenyl, C₃-C₆ alkynyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl,C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-C₆ (alkylthio)carbonyl,C₂-C₆ alkoxy(thiocarbonyl), C₄-C₈ cycloalkylcarbonyl, C₄-C₈cycloalkoxycarbonyl, C₄-C₈ (cycloalkylthio)carbonyl or C₄-C₈cycloalkoxy(thiocarbonyl); or a pair of R^(23a) and R^(23b) attached tothe same nitrogen atom are taken together with the nitrogen atom to forma 3- to 6-membered heterocyclic ring, the ring optionally substitutedwith up to 5 substituents independently selected from R²⁶; each R²⁴ andR²⁵ is independently H, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl,C₃-C₆ alkynyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₂-C₆alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-C₆ (alkylthio)carbonyl, C₂-C₆alkoxy(thiocarbonyl), C₄-C₈ cycloalkylcarbonyl, C₄-C₈cycloalkoxycarbonyl, C₄-C₈ (cycloalkylthio)carbonyl or C₄-C₈cycloalkoxy(thiocarbonyl); each R²⁶ is independently halogen, C₁-C₆alkyl, C₁-C₆ haloalkyl or C₁-C₆ alkoxy; each u and v are independently0, 1 or 2 in each instance of S(═O)_(u)(═NR¹⁴)_(v), provided that thesum of u and v is 0, 1 or 2; each w is independently 0, 1 or 2; and eachy is independently 0, 1 or 2; provided that: (a) when Q² is a phenylring substituted on at least one ortho position with a substituentselected from —U—V-T wherein U is a direct bond and T is NR^(23a)R^(23b)or OR²⁴, then V is other than C(═O); and (b) when Q¹ is phenyl and Q² is4-(trifluoromethyl)phenyl, then R² is other than methyl.